JP2009069793A - Process of producing patterned birefringent product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process of readily producing a patterned birefringent product excellent in resolution and heat-resistance and to provide a material. <P>SOLUTION: The process comprises at least the following steps [1] to [3] in order: [1] preparing a birefringence pattern builder which comprises an optically anisotropic layer comprising a polymer and having a retardation disappearance temperature in the range higher than 20°C at which in-plane retardation becomes 30% or lower of the retardation at 20°C, and rising by light exposure; [2] subjecting the birefringence pattern builder to patterned light exposure; and [3] heating the laminated structure obtained after the step [2] at 50 °C or higher and 400°C or lower. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an article having a birefringence pattern, and an article such as a substrate for a liquid crystal display device obtained by the method.

Conventionally, the birefringence pattern has been used in various forms in the industry.
In Patent Document 1, the use of a birefringence pattern as an image recording method is proposed, and a birefringence pattern that cannot be generally identified by human eyes is visualized by sandwiching it between two polarizing plates. A technique that positively utilizes the feature of the birefringence pattern “originally invisible but visualized by a polarizing plate” is disclosed in Patent Document 2, and in this document, an authentic authentication image of the birefringence pattern is disclosed. Use is proposed.

Conventionally, reflection holograms have been used exclusively in the field of authentication images. Holograms are suitable as authentication images because they can be easily determined by visual inspection and simple copying using a copying machine or the like is difficult. However, with the spread of technology in recent years, the production of holograms has become easier, and imitations that are indistinguishable from authentic holograms have become relatively easy to produce. In order to avoid forgery, it is possible to employ a structure that more accurately detects the direction and intensity of diffracted light using a machine, but visual identification becomes difficult.
On the other hand, since the birefringence pattern can be easily identified by using a polarizing plate and the manufacturing technique is hardly spread, forgery is difficult and suitable as an authentication image.

The birefringence pattern can also be used for a diffraction grating, a binary lens, or the like, which is an optical element produced by a refractive index pattern. By using the birefringence pattern, it is possible to produce a polarization separation element that exhibits an effect as an optical element only for desired polarization, and application to the projector and optical communication fields can be expected.
Further, the birefringence pattern can be applied to information recording materials. So-called photopolymers record information in the form of density and refractive index, whereas birefringence pattern information is recorded in the form of birefringence. Whereas the density and refractive index are scalar quantities having only magnitude, the birefringence is a vector quantity having magnitude and direction, so that higher density information recording can be expected.
Further, as an application example of a birefringence pattern, use in a stereoscopic image display device has been studied (Patent Document 3).

As a method for producing a birefringence pattern, several methods have been proposed so far.
One method is to use heat. For example, in Patent Document 1 described above, a method is used in which anisotropy film is heated by using a heat mode laser or a thermal head to heat the image forming portion to completely or partially reduce anisotropy. Moreover, in patent document 2, the method of thermally relaxing orientation using the stamp and laser which have a heating pattern with respect to retardation film is used. Furthermore, in patent document 3, the method of using the heating member which has a convex part with respect to retardation film selectively lose | disappears retardation is used.

  However, any of the patterns produced by the technique for reducing the birefringence using heat as described above has a drawback that it is inferior in heat resistance. That is, when heat is applied to a portion where birefringence remains, the birefringence of the portion may be lowered. Further, since it is difficult to make a difference between the heat transfer in the film thickness direction and the heat transfer in the in-plane direction with the technique using a thermal head or a heat stamp, it is extremely difficult to draw a pattern with a resolution less than the film thickness. Heating using a laser enables high resolution pattern drawing, but there is a problem that processing takes a long time because a fine pattern is drawn by laser scanning.

  Patent Document 1 also proposes a method of reducing birefringence by light using a photodisintegrating photopolymer or a photoisomerizable polymer. However, in the case of this method, the light resistance of the produced pattern is low, and it is not suitable as a birefringence pattern used as an optical element.

  As another method for producing a birefringence pattern, pattern exposure through a photomask is performed in a state in which a coating liquid containing a polymerizable liquid crystal and a polymerization initiator is applied and aligned on a support having an alignment film. A method has been proposed in which the orientation of the polymer is fixed by polymerization, further heated to make the unexposed portion isotropic, then exposed again, and optical anisotropy appears only in the first exposed portion. (Patent Document 4, Non-Patent Document 1). However, in this method, in order to control the alignment state of the liquid crystal before fixing, it is necessary to perform multiple exposures while exquisitely controlling the temperature of the entire system, and there is a problem that the manufacturing process is troublesome.

Furthermore, the production of birefringence patterns can be expected to be applied in the field of liquid crystal display devices.
A CRT (Cathode Ray Tube) has been mainly used so far as a display device used for OA equipment such as a word processor, a notebook personal computer and a personal computer monitor, a portable terminal, and a television. In recent years, liquid crystal display devices (LCDs) have been widely used instead of CRTs because of their thinness, light weight, and low power consumption. The liquid crystal display device has a liquid crystal cell and a polarizing plate. The polarizing plate comprises a protective film and a polarizing film, and is obtained by dyeing a polarizing film made of a polyvinyl alcohol film with iodine, stretching, and laminating both surfaces with a protective film. For example, in a transmissive LCD, this polarizing plate is attached to both sides of a liquid crystal cell, and an optical compensation sheet having one or more optically anisotropic layers may be disposed. On the other hand, in a reflective LCD, a reflector, a liquid crystal cell, one or more optical compensation sheets, and a polarizing plate are arranged in this order. The liquid crystal cell includes a liquid crystal molecule, two substrates for encapsulating the liquid crystal molecule, and an electrode layer for applying a voltage to the liquid crystal molecule. The liquid crystal cell performs ON / OFF display depending on the alignment state of liquid crystal molecules, and can be applied to both transmission type and reflection type. TN (Twisted Nematic), IPS (In-Plane Switching), OCB (Optically Compensatory). Display modes such as Bend), VA (Vertically Aligned), ECB (Electrically Controlled Birefringence), and STN (Super Twisted Nematic) have been proposed.

  More recently, LCDs have been widely used as display devices for mobile applications such as mobile phones and digital cameras, taking advantage of their thin, lightweight, and low power consumption characteristics. Mobile applications require not only indoor use but also outdoor use or long-term use without power supply, so indoors use transmissive display using a backlight, and outdoor use without using a backlight to reflect using external light. It is desirable to use a transflective LCD that can display. However, a transflective LCD having both transmissive display and reflective display in one pixel requires an optical compensation sheet that satisfies both transmission / reflection requirements, so two or more optical compensation sheets are bonded at various angles. Many things are needed, such as thicker LCDs, expensive roll-to-roll bonding, making the optical compensation sheet laminate expensive, and varying angles of optical compensation sheets It was causing.

In order to solve this problem, a method of forming an optically anisotropic layer only on the reflective portion of a transflective LCD has been proposed (Non-Patent Document 2). In this method, the alignment direction of the polymerizable liquid crystalline compound to be aligned is rotated by rotating the polarization direction of the irradiated polarized ultraviolet ray by 45 degrees in the first exposure with the photomask and the second entire exposure with respect to the photo-alignment film. The method of changing is used. This proposal eliminates the need for an optical compensation sheet for a transflective LCD and can achieve a significant reduction in the thickness of the LCD. However, three times of UV irradiation, including two times of polarized UV irradiation, a photo-alignment film layer and a polymerizable liquid crystal layer. Is required to be applied twice, so that the process load is too large, and it has not been put into practical use. In this technique, the two alignment domains must have the same retardation, which limits the degree of freedom in switching design of the LCD.
JP-A-3-141320 JP 2007-1130 A JP 2005-37736 A British Patent No. 2394718A Advanced Functional Materials, 791-798,16,2006 SID Symposium Digest 34, 194 (2003

    An object of the present invention is to provide a method and a material useful for simple production of an article having a birefringence pattern having high resolution and excellent heat resistance. Another object of the present invention is to provide a method and a material for producing a pattern that is substantially colorless and transparent when observed through a polarizing plate and can be easily identified by observation through a polarizing plate. Furthermore, the present invention aims to provide a useful method for producing a substrate for a liquid crystal display device having a patterned retardation, and reduces the number of optical compensation sheets of an LCD, particularly a transflective LCD, An object of the present invention is to provide a substrate for a liquid crystal display device that contributes to reducing the thickness of an LCD.

That is, the present invention provides the following (1) to (29).
(1) Manufacturing method of article having birefringence pattern including at least the following steps [1] to [3] in this order:
[1] An optically anisotropic layer containing a polymer,
The optically anisotropic layer has a retardation disappearing temperature at which the in-plane retardation is 30% or less of the retardation at 20 ° C. in a temperature range higher than 20 ° C., and the retardation disappearing temperature is increased by exposure. Preparing a birefringence pattern builder material;
[2] A step of performing pattern exposure on the birefringence pattern builder;
[3] A step of heating the laminate obtained after step 2 to 50 ° C. or higher and 400 ° C. or lower.

(2) The production method according to (1), wherein the rising retardation disappearance temperature of the birefringence pattern builder is not in a temperature range of 250 ° C. or lower.
(3) The production method according to claim 1 or 2, wherein the in-plane retardation at 20 ° C of the birefringence pattern builder is 10 nm or more.
(4) The production method according to any one of claims 1 to 3, wherein the polymer has an unreacted reactive group.
(5) The optically anisotropic layer is formed by applying and drying a solution containing a liquid crystal compound having at least one reactive group to form a liquid crystal phase, and then polymerizing and fixing by irradiation with heat or ionizing radiation. (1) The manufacturing method of any one of (4).

(6) The production method according to (5), wherein the liquid crystalline compound has two or more reactive groups having different polymerization conditions.
(7) The production method according to (5), wherein the liquid crystal compound has at least a radical reactive group and a cationic reactive group.
(8) The production method according to (7), wherein the radical reactive group is an acryl group and / or a methacryl group, and the cationic group is a vinyl ether group, an oxetane group and / or an epoxy group.

(9) The manufacturing method according to any one of claims 1 to 4, wherein the optically anisotropic layer is made of a stretched film.
(10) The manufacturing method according to any one of (1) to (9), including two or more optically anisotropic layers.
(11) The production method according to (10), wherein the two or more optically anisotropic layers include at least two optically anisotropic layers having different slow axis directions and / or in-plane retardation.

(12) Any one of (1) to (11), wherein the optically anisotropic layer is a layer provided by transferring a transfer material including the optically anisotropic layer onto a material to be transferred. The manufacturing method as described in.
(13) The manufacturing method according to any one of (1) to (12), including the following steps 13 and 14 in this order after the step 2 and before the step 3:
[13] A step of transferring another birefringence pattern builder to the laminate obtained after step 2;
[14] A step of performing pattern exposure on the laminate obtained after the transfer.

(14) The manufacturing method according to any one of (1) to (12), which includes the following steps 24 to 26 in this order after the step 3:
[24] A step of transferring another birefringence pattern builder to the laminate obtained after step 3;
[25] A step of performing pattern exposure on the laminate obtained after step 24;
[26] A step of heating the laminate obtained after step 25 to 50 ° C. or higher and 400 ° C. or lower.
(15) The birefringence pattern builder has a photosensitive resin layer on an optically anisotropic layer, and the birefringence pattern builder is subjected to pattern exposure from the photosensitive resin layer side in the step 2, and The manufacturing method of any one of (1)-(12) including the following process 9 after the process 2:
[9] A step of removing an unnecessary photosensitive resin layer on the laminate.

(16) An article used as a forgery prevention means obtained by the production method according to any one of (1) to (15).
(17) An optical element obtained by the manufacturing method according to any one of (1) to (15).
(18) A substrate for a liquid crystal display device obtained by the production method according to any one of (1) to (15).
(19) A method for manufacturing a substrate for a liquid crystal display device including at least the following steps [101] to [103] in this order:
[101] A liquid crystal compound having at least one reactive group on a substrate is coated and dried to form a liquid crystal phase, and then the liquid crystal phase is irradiated with heat or ionizing radiation to form an optically anisotropic layer. [102] Step of pattern exposure of the optically anisotropic layer [103] Step of heating the optically anisotropic layer to 50 ° C. or higher and 400 ° C. or lower.

(20) A method for manufacturing a substrate for a liquid crystal display device including at least the following steps [111] to [115] in this order:
[111] A solution containing a liquid crystal compound having at least one reactive group is applied onto a substrate and dried to form a liquid crystal phase, and then the liquid crystal phase is irradiated with heat or ionizing radiation to form an optically anisotropic layer. [112] Step of forming a photosensitive resin layer on the optically anisotropic layer [113] Step of pattern exposure of the optically anisotropic layer and photosensitive resin layer [114] Unnecessary on the substrate [115] The process of heating this optically anisotropic layer to 50 degreeC or more and 400 degrees C or less.

(21) A method for manufacturing a substrate for a liquid crystal display device including at least the following steps [121] to [123] in this order:
[121] An optically anisotropic layer obtained by applying and drying a solution containing a liquid crystalline compound having at least one reactive group to form a liquid crystal phase, and then irradiating the liquid crystal phase with heat or ionizing radiation. A step of forming a transfer adhesive layer and an optically anisotropic layer on the substrate in this order using a transfer material having a transfer adhesive layer. [122] a step of pattern exposing the optically anisotropic layer [123] Heating the optically anisotropic layer to 50 ° C. or higher and 400 ° C. or lower.

(22) A method for manufacturing a substrate for a liquid crystal display device, comprising at least the following steps [131] to [135] in this order:
[131] An optically anisotropic layer obtained by applying and drying a solution containing a liquid crystalline compound having at least one reactive group to form a liquid crystal phase and then irradiating the liquid crystal phase with heat or ionizing radiation; Forming a transfer adhesive layer and an optically anisotropic layer in this order on a substrate using a transfer material having a transfer adhesive layer;
[132] A step of forming a photosensitive resin layer on the optically anisotropic layer;
[133] A step of pattern exposing the optically anisotropic layer and the photosensitive resin layer;
[134] A step of removing an unnecessary photosensitive resin layer on the substrate;
[135] A step of heating the optically anisotropic layer to 50 ° C. or higher and 400 ° C. or lower.

(23) A method of manufacturing a substrate for a liquid crystal display device including at least the following steps [521] to [523] in this order:
[521] A step of forming a transfer adhesive layer and an optical anisotropic layer in this order on a substrate using a transfer material having an optically anisotropic layer made of a stretched film and a transfer adhesive layer. [522] Step of pattern exposure of optically anisotropic layer [523] A step of heating the optically anisotropic layer to 50 ° C. or higher and 400 ° C. or lower.

(24) Manufacturing method of substrate for liquid crystal display device including at least the following steps [531] to [535] in this order:
[531] A step of forming a transfer adhesive layer and an optical anisotropic layer in this order on a substrate using a transfer material having an optically anisotropic layer made of a stretched film and a transfer adhesive layer. [532] The optical Step of forming photosensitive resin layer on anisotropic layer [533] Step of pattern exposure of optically anisotropic layer and photosensitive resin layer [534] Step of removing unnecessary photosensitive resin layer on substrate [535] A step of heating the optically anisotropic layer to 50 ° C. or higher and 400 ° C. or lower.

(25) A substrate for a liquid crystal display device obtained by the production method according to any one of (19) to (24).
(26) The substrate for a liquid crystal display device according to (18) or (25), comprising an optically anisotropic layer having a region of in-plane retardation Re1 and a region of in-plane retardation Re2 (where Re1> Re2).
(27) The substrate for liquid crystal display device according to (26), wherein Re2 is 5 nm or less.
(28) A liquid crystal display device comprising the substrate for a liquid crystal display device according to any one of (25) to (27).
(29) The liquid crystal display device according to (28), wherein the liquid crystal mode is a transflective mode.

The present invention also provides the following birefringence pattern builder (201) to (212).
(201) including an optically anisotropic layer containing a polymer,
The optically anisotropic layer has a retardation disappearance temperature at which the in-plane retardation is 30% or less of the retardation at 20 ° C in a temperature range higher than 20 ° C, and the retardation disappearance temperature is increased by exposure. Birefringence pattern builder.
(202) The birefringence pattern builder according to (201), wherein the retardation disappearance temperature after the rise is not in a temperature range of 250 ° C. or lower.

(203) The birefringence pattern builder according to (201) or (202), wherein the in-plane retardation at 20 ° C. is 10 nm or more.
(204) The birefringence pattern builder according to any one of (201) to (203), wherein the polymer has an unreacted reactive group.
(205) The optically anisotropic layer is formed by applying and drying a solution containing a liquid crystalline compound having at least one reactive group to form a liquid crystal phase, and then polymerizing and fixing by irradiation with heat or ionizing radiation. The birefringence pattern builder according to any one of (201) to (204).
(206) The birefringence pattern builder according to (205), wherein the liquid crystalline compound has two or more reactive groups having different polymerization conditions.

(207) The birefringence pattern builder according to (205), wherein the liquid crystalline compound has at least a radical reactive group and a cationic reactive group.
(208) The birefringence pattern builder according to (207), wherein the radical reactive group is an acryl group and / or a methacryl group, and the cationic group is a vinyl ether group, an oxetane group and / or an epoxy group. .
(209) The birefringence pattern builder according to any one of (201) to (204), wherein the optically anisotropic layer is made of a stretched film.
(210) The birefringence pattern builder according to any one of (201) to (209), which includes two or more optically anisotropic layers.

(211) The birefringence pattern production according to (210), wherein the two or more optically anisotropic layers include at least two optically anisotropic layers having different slow axis directions and / or in-plane retardations. material.
(212) Any one of (201) to (211), wherein the optically anisotropic layer is a layer provided by transferring a transfer material including the optically anisotropic layer onto a transfer material. Birefringence pattern builder as described in

The present invention further provides the following (30) to (31) as a preferred embodiment for the above production method.
(30) A method for producing an article having a birefringence pattern including at least the following steps [211] to [215] in this order:
[211] A step of preparing a birefringence pattern builder according to any one of (201) to (212);
[212] A step of performing pattern exposure on the birefringence pattern builder;
[213] A step of transferring another birefringence pattern builder to the laminate obtained after step 212;
[214] Performing pattern exposure on the laminate obtained after step 213;
[215] A step of heating and baking the laminate obtained after step 214 to 50 ° C. or more and 400 ° C. or less.

(31) A method for producing an article having a birefringence pattern including at least the following steps [221] to [226] in this order:
[221] A step of preparing a birefringence pattern builder according to any one of (201) to (212);
[222] A step of performing pattern exposure on the birefringence pattern builder;
[223] A step of heating the laminate obtained after step 222 to 50 ° C or higher and 400 ° C or lower;
[224] A step of transferring any one of the birefringence pattern builder onto the laminate obtained after the step 223;
[225] A step of performing pattern exposure on the laminate obtained after step 224;
[226] A step of heating the laminate obtained after step 225 to 50 ° C. or higher and 400 ° C. or lower.

  By using the materials and methods of the present invention, an article having a heat-resistant, high-resolution birefringence pattern can be obtained. The birefringence pattern is almost colorless and transparent when not passing through the polarizing plate, but can be easily identified by passing through the polarizing plate, and is effective in preventing forgery and imparting a visual effect. In addition, an optically anisotropic layer having a patterned retardation can be provided in a liquid crystal cell with almost no increase in the number of manufacturing steps of the liquid crystal display device by the method for manufacturing a substrate for a liquid crystal display device using the above article. As compared with the conventional transflective LCD, a significant reduction in thickness can be achieved. In particular, when a transfer material is used, the cost can be reduced by reducing the number of steps. Furthermore, a transflective LCD having a color filter substrate manufactured by the above manufacturing method greatly contributes to reduction in thickness and improvement in viewing angle characteristics.

Hereinafter, the present invention will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

  In the present specification, retardation or Re represents in-plane retardation. In-plane retardation (Re (λ)) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments). Retardation or Re in this specification means those measured at wavelengths of 611 ± 5 nm, 545 ± 5 nm, and 435 ± 5 nm for R, G, and B, respectively. It means that measured at a wavelength of 5 nm or 590 ± 5 nm.

  In this specification, “substantially” for the angle means that the error from the exact angle is within a range of less than ± 5 °. Furthermore, the error from the exact angle is preferably less than 4 °, more preferably less than 3 °. With regard to retardation, “substantially” means that the retardation is within ± 5%. Furthermore, Re is not substantially 0 means that Re is 5 nm or more. In addition, the measurement wavelength of the refractive index indicates an arbitrary wavelength in the visible light region unless otherwise specified. In the present specification, “visible light” refers to light having a wavelength of 400 to 700 nm.

  In the present specification, the “retardation disappearance temperature” means the retardation of the optically anisotropic layer at a certain temperature when the temperature of the optically anisotropic layer is increased from 20 ° C. at a rate of 20 ° C. per minute. Means a temperature at which the retardation of the optically anisotropic layer at 20 ° C. is 30% or less.

  In the present specification, “the retardation disappearance temperature is not in a temperature range of 250 ° C. or lower” means that the letter of the optical anisotropic layer is not increased even when the temperature of the optical anisotropic layer is raised to 250 ° C. It means that the foundation does not become 30% or less of the retardation at 20 ° C.

[Birefringence pattern builder]
FIG. 1 is a schematic cross-sectional view of several examples of a birefringence pattern builder. The birefringence pattern builder is a material for producing a birefringence pattern, and is a material capable of producing an article having a birefringence pattern through a predetermined process. The birefringence pattern builder shown in FIG. 1A is an example having an optically anisotropic layer 12 on a support (substrate) 11. The birefringence pattern builder shown in FIG. 1B is an example having an alignment layer 13. When the alignment layer 13 is formed by applying and drying a solution containing a liquid crystal compound as the optically anisotropic layer 12 to form a liquid crystal phase and then polymerizing and fixing by irradiation with heat or ionizing radiation, the liquid crystal compound is used. Functions as a layer to help the orientation of the film.

The birefringence pattern builder shown in FIG. 1C is an example in which a reflective layer 35 is further provided on the support 11. The birefringence pattern builder shown in FIG. 1D is an example having a reflective layer 35 under the support 11. The birefringence pattern builder shown in FIG. 1 (e) is an example having a rear adhesive layer 16 and a release layer 17 under the support for further pasting on another article after the birefringence pattern is created. The birefringence pattern builder shown in FIG. 1 (f) is an example having a transfer adhesive layer 14 between the support 11 and the optically anisotropic layer 12 because it is made of a transfer material. The birefringence pattern builder shown in FIG. 1G is an example having a plurality of optically anisotropic layers (12F, 12S). The birefringence pattern builder shown in FIG. 1H is an example having a reflective layer 35 under the self-supporting optically anisotropic layer 12. The birefringence pattern builder shown in FIG. 1 (i) is an example having a rear adhesive layer 16 and a release layer 17 below the reflective layer 35 for further pasting on another article after pattern formation.

[Birefringence pattern builder used as transfer material]
FIG. 2 is a schematic sectional view of several examples of the birefringence pattern material of the present invention used as a transfer material. By using a birefringence pattern builder as a transfer material, a birefringence pattern builder having an optically anisotropic layer on a desired support, a birefringence pattern builder having a plurality of optically anisotropic layers, or birefringence An article having a plurality of layers having a pattern can be easily manufactured.

  The birefringence pattern builder shown in FIG. 2A is an example having the optically anisotropic layer 12 on the temporary support 21. The birefringence pattern builder shown in FIG. 2B is an example in which a transfer adhesive layer 14 is further provided on the optically anisotropic layer 12. The birefringence pattern builder shown in FIG. 2C is an example in which a surface protective layer 18 is further provided on the transfer adhesive layer 14. The birefringence pattern builder shown in FIG. 2D is an example in which an alignment layer 22 on the temporary support 21 is further provided between the temporary support 21 and the optically anisotropic layer 12. The birefringence pattern builder shown in FIG. 2 (e) is an example in which a mechanical property control layer 23 is further provided between the temporary support 21 and the alignment layer 22 on the temporary support. The birefringence pattern builder shown in FIG. 2F is an example having a plurality of optically anisotropic layers (12F, 12S).

[Article having birefringence pattern]
FIG. 3 is a schematic cross-sectional view of some examples of articles having a birefringence pattern obtained by a production method using a birefringence pattern builder. An article having a birefringence pattern obtained by the method of the present invention has at least one patterned optically anisotropic layer 112. In the present specification, the “patterned optically anisotropic layer” means “an optically anisotropic layer having regions having different birefringence in a pattern”. The article having the birefringence pattern shown in FIG. 3A is an example including only the patterned optically anisotropic layer 112. The exposed portion 112-A and the unexposed portion 112-B shown in the figure have different birefringence. The article having the birefringence pattern shown in FIG. 3B is an example having the reflective layer 35, the transfer adhesive layer 146, and the patterned optically anisotropic layer 112 in this order on the support 11 from the support side. An article having a birefringence pattern may have a plurality of patterned optically anisotropic layers, and more various functions can be exhibited by having a plurality of optically anisotropic layers. The article having the birefringence pattern shown in FIG. 3C is an example in which the same pattern is given by pattern exposure after laminating a plurality of optically anisotropic layers. Such an example is useful, for example, for producing a pattern including a region having a large retardation that cannot be produced by a single optically anisotropic layer. In the article having the birefringence pattern shown in FIG. 3D, “optically anisotropic layer formation (including transfer) → pattern exposure → bake” is repeated a plurality of times to give independent patterns to the plurality of optically anisotropic layers. This is an example. For example, this is a useful example when two or more optically anisotropic layers having different retardation or slow axis directions are provided and independent patterns are desired. The birefringence pattern shown in FIG. 3 (e) is an example in which patterning is performed by a single baking after the necessary number of optical anisotropic layer formation (including transfer) and pattern exposure are alternately performed. By the same method, the necessary number of regions having different retardations can be produced while minimizing the number of bakings with a large process load.

[Liquid crystal display substrate]
The substrate for a liquid crystal display device obtained by the production method of the present invention is a substrate for a liquid crystal display device having a patterned retardation, and includes a substrate and an optically anisotropic layer having at least one pattern of retardation. Have. In the present specification, “an optically anisotropic layer having a patterned retardation” means “an optically anisotropic layer having a region having a different retardation in a pattern”, and usually “an in-plane retardation Re1 region”. And an optically anisotropic layer having a pattern of in-plane retardation Re2 (where Re1> Re2). In the present specification, unless otherwise specified, “a substrate for a liquid crystal display device” and “a substrate” are usually used separately.

  FIG. 4 is a schematic cross-sectional view of several examples of a substrate for a liquid crystal display device obtained by the production method of the present invention. The substrate for a liquid crystal display device shown in FIG. 4A is obtained by forming an optically anisotropic layer 12 having a patterned retardation on a substrate 11. The substrate 11 is not particularly limited as long as it is transparent, but a support having a small birefringence is desirable, and glass, a low birefringence polymer, or the like is used. The optically anisotropic layer 12 having a patterned retardation is coated with a solution containing a liquid crystal compound on a substrate, ripened and oriented at a liquid crystal phase forming temperature, and then irradiated with heat or ionizing radiation in that state. The optically anisotropic layer obtained by solidifying can be obtained by pattern exposure and heating. An optically anisotropic layer having a patterned retardation is formed between the exposed portion 12A and the unexposed portion 12B of the optically anisotropic layer 12 due to the difference in retardation caused by the heating process. This makes it possible to achieve different optical compensations in different display modes in the liquid crystal cell, particularly in the transmissive part and reflective part of the transflective LCD. Furthermore, unlike the conventional case where an optically anisotropic layer is provided on a plastic support that easily changes in size due to temperature and humidity, if an optically anisotropic layer is provided in a cell, the optically anisotropic layer Since it is firmly held by the glass substrate, the dimensional change due to temperature and humidity hardly occurs, and the corner unevenness of the LCD can be improved. The pattern exposure method may be direct exposure using a commercially available laser drawing apparatus or the like as long as there is a difference in exposure amount and resolution required between the exposed portion and the unexposed portion, or exposure through a photomask.

  In the liquid crystal display device substrate shown in FIG. 4B, an alignment layer 13 is formed between the substrate 11 and the optically anisotropic layer 12. A solution containing a liquid crystal compound is applied directly onto the rubbed alignment layer 13, then aged and aligned at the liquid crystal phase formation temperature, and solidified by irradiation with heat or ionizing radiation in this state. Layer 12 is formed. Formation of regions having different retardations can be performed in the same manner as described above. In the substrate for a liquid crystal display device shown in FIG. 4C, a transfer adhesive layer 14 is formed between the substrate 11 and the optically anisotropic layer 12 having a patterned retardation. This embodiment can be manufactured using a transfer material as shown in FIG. The substrate for a liquid crystal display device shown in FIGS. 4D and 4E is a mode having a photosensitive resin layer 15 on the optically anisotropic layer 12. In FIG. 4D, a negative type photosensitive resin is used, and in FIG. 4E, a positive type photosensitive resin is used. In either case, a concavo-convex pattern can be formed simultaneously with exposure for patterning a phase difference. This embodiment can be produced, for example, by directly applying the photosensitive resin layer 15 on FIG. 4C or using a transfer material as shown in FIG.

[Transfer materials (examples used for substrates for liquid crystal display devices)]
FIG. 5A shows an example of a transfer material, in which an optically anisotropic layer 12 is formed on a temporary support 21 via an alignment layer 22. A transfer adhesive layer 14 is formed on the optically anisotropic layer 12, and a substrate for a liquid crystal display device can be produced by laminating and transferring a transfer material to the substrate via the transfer adhesive layer 14. The adhesive layer for transfer is not particularly limited as long as it has sufficient transferability, and examples thereof include a pressure-sensitive adhesive layer, a photosensitive resin layer, a pressure-sensitive resin layer, and a heat-sensitive resin layer. A photosensitive or heat-sensitive resin layer is desirable because of the bake resistance necessary for the substrate for the apparatus. In order to provide good transferability, it is desirable that the peelability between the optically anisotropic layer 12 and the alignment layer 22 is high. FIG. 5B shows an embodiment having a mechanical property control layer 23 for preventing air bubbles from being mixed in the transfer process and absorbing irregularities on the substrate for the liquid crystal display device. As the mechanical property control layer, a layer exhibiting flexible elasticity, a layer softened by heat, a layer exhibiting fluidity by heat, or the like is preferable. FIG. 5 (c) shows a transfer material that can produce FIG. 4 (d) or (e). A photosensitive resin layer 15 for forming irregularities is provided under the optically anisotropic layer 12. In order to produce this embodiment, it is necessary to orient the liquid crystalline compound on the photosensitive resin layer 15. Usually, a coating liquid containing a liquid crystalline compound is used on the photosensitive resin layer using an organic solvent. When applied, the photosensitive resin layer is dissolved by the organic solvent, so that the liquid crystalline compound cannot be aligned. Therefore, a transfer material as shown in FIG. 5D is formed on another temporary support 24, and the photosensitive resin layer 15 also serves as a transfer adhesive layer for the temporary support 21. It can be produced by forming the transfer adhesive layer 14 thereon.

[Substrate for liquid crystal display device (substrate having color filter layer)]
FIG. 6A is a schematic cross-sectional view of an example of a substrate for a liquid crystal display device obtained by the production method of the present invention and having a color filter layer. In this example, a color filter substrate having a color filter layer on a substrate made of the above-described glass or low birefringence polymer is used as the substrate. The substrate for a liquid crystal display device of the present invention has a color filter layer having a lower process temperature than the liquid crystal display device substrate on the side having the TFT layer, out of the two liquid crystal display device substrates forming the liquid crystal cell. It is preferably used as a substrate for a liquid crystal display device. In the substrate for a liquid crystal display device on the side having the color filter layer, a black matrix 31 is generally formed on the substrate, and a color filter may be formed thereon by a photolithography process. Furthermore, an optically anisotropic layer 12 having a patterned retardation is formed by producing a layer including an optically anisotropic layer directly or from a transfer material, followed by pattern exposure or the like, followed by a heating step. The FIG. 6A shows a cross-sectional view and a top view. In the case of a transflective LCD, the transmissive part 33 and the reflective part 34 are provided in one pixel composed of RGB. A pattern may be formed partially or in stripes on the color filter. The transmissive part 33 and the reflective part 34 may be reversed, but in the case of a transflective LCD, since only the transmissive part can be optically compensated on the backlight side of the liquid crystal cell, retardation is applied only to the reflective part. It is preferable that the optical compensation can greatly contribute to the performance improvement. FIG. 6B shows an example in which a step layer made of a photosensitive resin layer is further formed. Thus, the substrate for a liquid crystal display device of the present invention can change the height between the transmissive portion 33 and the reflective portion 34, thereby enabling a so-called multigap that changes the liquid crystal cell gap. Although FIG. 6B has protrusions in the reflection part, in general, in a transflective LCD, since the cell gap of the reflection part is smaller than that of the transmission part, an aspect having protrusions in the reflection part is preferable. In the reverse case, the photosensitive resin layer may be a positive type.

  The substrate for a liquid crystal display device of the present invention is effective even when used for a transmissive LCD. FIG. 6C shows a mode in which a transmissive LCD is assumed. In FIG. 6C, R and G are exposed areas, B is an unexposed area, and retardation on B is small or substantially zero. Since the optimum values of retardation for optical compensation for R, G and B are generally different, the retardation can be adjusted for each RGB color by the substrate for a liquid crystal display device of the present invention. The substrate for a liquid crystal display device of the present invention can be combined with a general optical compensation sheet, and a further viewing angle improvement effect, particularly a color viewing angle improvement effect can be expected. FIG. 6D shows a mode in which the cell gap is also controlled for each RGB. This multi-gap can further improve the color viewing angle characteristics of the LCD, and achieve high-quality LCD display characteristics in combination with the RGB independent retardation control of the present invention.

  When the liquid crystal display device substrate of the present invention is used as the liquid crystal display device substrate on the side having the TFT layer, the optically anisotropic layer may be formed at any position, but the TFT array process is usually performed at 300 ° C. for silicon formation. Since the above high temperature process is required, in the case of an active drive type having a TFT, the optically anisotropic layer is preferably above the silicon layer of the TFT.

[Liquid Crystal Display]
FIG. 7 is a schematic cross-sectional view of an example of a liquid crystal display device including the substrate for a liquid crystal display device of the present invention. The example of FIG. 7A is a transflective liquid crystal display device using FIG. 6B as the liquid crystal display substrate 48 on the side having the color filter layer. Two polarizing plates 49 composed of protective films 42 and 43 sandwiching the polarizing layer 41 are bonded to the upper and lower liquid crystal display substrate 11 forming a liquid crystal cell via an adhesive 44, respectively. In general, a driving element 45 such as a TFT is formed on a liquid crystal display substrate on the lower side of a liquid crystal cell. Is formed. Liquid crystal 47 is filled between liquid crystal display substrate substrates above and below the liquid crystal cell, and the liquid crystal display device is switched by changing the orientation of the liquid crystal by applying a voltage. In general, an alignment film (not shown in the drawing) is formed on the uppermost surfaces of the upper and lower substrates for the liquid crystal display device in order to determine the alignment of the liquid crystal 47, and the upper surface is rubbed. The liquid crystal cell gap of the reflection part can be controlled to a gap different from that of the transmission part by the step formed by the reflection plate 46 and the photosensitive resin layer 15. Of the two protective films sandwiching the polarizing layer, 43 may be an optical compensation sheet, or a normal protective film 42 may be used. The viewing angle of the transmissive part is controlled by the upper and lower optical compensation sheets 43, and the viewing angle of the reflective part is controlled by the upper compensation sheet 43 and the optically anisotropic layer 12A in the cell.

FIG. 7B shows an example of a transflective LCD using only an optical compensation sheet as a comparative example. 43A is a λ / 2 plate, 43B is a λ / 4 plate, and 43A and 43B have a wideband λ / 4. Broadband λ / 4 plates are arranged on the top and bottom, the reflective part displays the reflective LCD display with the upper compensation sheet 43, and the upper broadband λ / 4 plate that is unnecessary for the transmissive LCD needs to be canceled with the lower polarizing plate There are four upper and lower compensation sheets.
The example of FIG. 7C is a transmission type liquid crystal display device using FIG. 6D as the liquid crystal display device substrate 48 on the side having the color filter layer. Each component other than the reflector 46 is the same as the transflective type, but in the case of the transmissive type, high-quality display characteristics are required in terms of image quality, particularly color, like a television. For this reason, it is desirable to design a liquid crystal cell optimized for each color filter RGB. Therefore, the optical compensation is performed by one or both of the upper and lower optical compensation sheets 43 constituting the polarizing plate 49 and the patterned optical anisotropic layer 12 in the cell, and the liquid crystal cell gap is also changed for each RGB. By using a multi-gap, it becomes possible to design a liquid crystal cell with a high degree of freedom. This method is preferable because an excellent viewing angle characteristic can be achieved particularly in the VA mode or the IPS mode.

  The substrate for a liquid crystal display device manufactured by the manufacturing method of the present invention includes a substrate, an optically anisotropic layer having a patterned retardation, and a photosensitive resin layer forming a step. The substrate for a liquid crystal display device of the present invention is preferably used for producing a constituent member of the liquid crystal display device, but the application is not particularly limited. In this aspect, the optically anisotropic layer contributes to optical compensation of the cell of the liquid crystal display device, that is, contributes to widening the contrast viewing angle and eliminating image coloring of the liquid crystal display device.

  Hereinafter, a birefringence pattern builder, a method for producing an article having a birefringence pattern using the birefringence pattern, a material for the article having a birefringence pattern, a production method, and the like will be described in detail. However, the present invention is not limited to this embodiment, and other embodiments can be carried out with reference to the following description and conventionally known methods, and the present invention is limited to the embodiments described below. It is not something.

[Optically anisotropic layer]
The optically anisotropic layer in the birefringence pattern builder is a layer having optical characteristics that are not isotropic, in which there is even one incident direction in which Re is not substantially 0 when the phase difference is measured. The optically anisotropic layer has a retardation disappearance temperature. The retardation disappearance temperature is preferably greater than 20 ° C. and 250 ° C. or less, more preferably 40 ° C. to 245 ° C., further preferably 50 ° C. to 245 ° C., and 80 ° C. to 240 ° C. Is most preferred.

  Further, as the optically anisotropic layer in the birefringence pattern builder, an optically anisotropic layer whose retardation disappearing temperature is increased by exposing the birefringence pattern builder to light is used. As a result, there is a difference in the retardation disappearance temperature between the exposed area and the unexposed area, and the baking is performed at a temperature higher than the retardation disappearance temperature of the unexposed area and lower than the retardation disappearance temperature of the exposed area. Only the retardation of the exposed portion can be selectively lost. In this case, the increase in the retardation disappearance temperature due to exposure is preferably 5 ° C. or more in consideration of the efficiency of selective disappearance of only the retardation of the unexposed area and the robustness against temperature variations in the heating apparatus. More preferably, the temperature is at least 20 ° C, and particularly preferably at least 20 ° C. Further, it is preferable that the retardation disappearance temperature of the exposed portion is not in the temperature range of 250 ° C. or less because the retardation of the unexposed portion is easily lost.

  The optically anisotropic layer in the birefringence pattern builder includes a polymer. By including a polymer, different types of requirements such as birefringence, transparency, solvent resistance, toughness and flexibility can be met. The polymer in the optically anisotropic layer preferably has an unreacted reactive group. This is because it is considered that the unreacted reactive group reacts upon exposure to cause crosslinking of the polymer chain, and as a result, the retardation disappearance temperature is likely to increase.

The optically anisotropic layer is preferably solid at 20 ° C., more preferably at 30 ° C., and even more preferably at 40 ° C. It is because application | coating of another functional layer, the transcription | transfer and bonding on a support body are easy that it is solid at 20 degreeC.
In order to apply another functional layer, the optically anisotropic layer of the present invention preferably has solvent resistance. In this specification, “having solvent resistance” means that the retardation after immersion for 2 minutes in the target solvent is in the range of 30% to 170% of the retardation before immersion, more preferably 50% to 150%. %, Most preferably in the range of 80% to 120%. The target solvent is water, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, hexane, chloroform, ethyl acetate, preferably acetone, methyl ethyl ketone, cyclohexanone, propylene glycol. Among monomethyl ether acetate and N-methylpyrrolidone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, or a mixed solvent thereof is most preferable.

  The optically anisotropic layer may have a retardation of 5 nm or more at 20 ° C., preferably 10 nm or more and 10,000 nm or less, and most preferably 20 nm or more and 2000 nm or less. If the retardation is 5 nm or less, it may be difficult to form a birefringence pattern. If the retardation exceeds 10,000 nm, the error may increase and it may be difficult to achieve practical accuracy. For reference, exposure and baking under appropriate conditions for a birefringence pattern builder including an optically anisotropic layer having a retardation of 1 to 50 nm (for example, when the material shown in Example 1 of the present invention is used, 35 mJ (UV -Easiness of pattern identification when an article having a birefringence pattern produced by performing UV exposure in region A) and baking at 230 ° C. for 1 hour each time is visually observed under crossed Nicols (visibility) Table 1 shows the guideline for. In the present specification, “under crossed Nicols” means a state in which a sample is disposed between two polarizing plates stacked so that the absorption axes are substantially orthogonal.

The method for producing the optically anisotropic layer is not particularly limited, but a solution containing a liquid crystalline compound having at least one reactive group is applied and dried to form a liquid crystal phase, and then polymerized by irradiation with heat or ionizing radiation. Method of immobilizing and preparing; Method of stretching a layer in which a monomer having at least two or more reactive groups is polymerized and immobilizing; Stretching after introducing a reactive group into a polymer layer using a coupling agent A method; or a method of introducing a reactive group using a coupling agent after stretching a layer made of a polymer.
As will be described later, the optically anisotropic layer of the present invention may be formed by transfer.

As described above, the optically anisotropic layer functions as an optically anisotropic layer that compensates the viewing angle of the liquid crystal display device by being incorporated in the liquid crystal cell. Optically required for optical compensation in combination with other layers (for example, an optically anisotropic layer disposed outside the liquid crystal cell) as well as an aspect in which the optically anisotropic layer alone has sufficient optical compensation capability Embodiments satisfying the characteristics are also included in the scope of the present invention. In addition, the optically anisotropic layer of the transfer material does not need to satisfy the optical characteristics sufficient for the optical compensation capability. For example, the optical characteristics are obtained through an exposure process performed in the process of being transferred onto the substrate. It may be expressed or changed to finally exhibit optical characteristics necessary for optical compensation.
The thickness of the optically anisotropic layer in the liquid crystal display device substrate is preferably 0.1 to 20 μm, and more preferably 0.5 to 10 μm.

[Optically anisotropic layer formed by polymerizing and fixing a composition containing a liquid crystalline compound]
When producing a liquid crystal phase by applying and drying a solution containing a liquid crystalline compound having at least one reactive group as a method for producing an optically anisotropic layer, followed by irradiation with heat or ionizing radiation and fixing by polymerization Is described below. In this production method, it is easy to obtain an optically anisotropic layer having a thin film thickness and an equivalent retardation as compared with a production method of obtaining an optically anisotropic layer by stretching a polymer described later.

[Liquid crystal compounds]
In general, liquid crystal compounds can be classified into a rod type and a disk type from the shape. In addition, there are low and high molecular types, respectively. Polymer generally refers to a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, 2 pages, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a disk-like liquid crystal compound is preferably used. Two or more kinds of rod-like liquid crystalline compounds, two or more kinds of disc-like liquid crystalline compounds, or a mixture of a rod-like liquid crystalline compound and a disk-like liquid crystalline compound may be used. It is more preferable to use a rod-like liquid crystal compound or a disk-like liquid crystal compound having a reactive group since temperature change and humidity change can be reduced, and at least one of the reactive groups in one liquid crystal molecule is 2 or more. More preferably it is. The liquid crystal compound may be a mixture of two or more, and in that case, at least one preferably has two or more reactive groups.

  It is also preferable that the liquid crystal compound has two or more reactive groups having different polymerization conditions. In this case, it is possible to produce an optically anisotropic layer including a polymer having an unreacted reactive group by selecting conditions and polymerizing only a part of plural types of reactive groups. . The polymerization conditions used may be the wavelength range of ionizing radiation used for polymerization immobilization, or the difference in polymerization mechanism used, but preferably a radical reaction group and a cationic reaction that can be controlled by the type of initiator used. A combination of groups is good. A combination in which the radical reactive group is an acrylic group and / or a methacryl group and the cationic group is a vinyl ether group, an oxetane group and / or an epoxy group is particularly preferable because the reactivity can be easily controlled.

Examples of rod-like liquid crystalline compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Not only the above low-molecular liquid crystalline compounds but also high-molecular liquid crystalline compounds can be used. The polymer liquid crystal compound is a polymer compound obtained by polymerizing a rod-like liquid crystal compound having a low molecular reactive group. The rod-like liquid crystalline compound having a low-molecular reactive group that is particularly preferably used is a rod-like liquid crystalline compound represented by the following general formula (I).
Formula (I): Q ¹ -L ¹ -A ¹ -L ³ -ML ⁴ -A ² -L ² -Q ²
In the formula, Q ¹ and Q ² are each independently a reactive group, and L ¹ , L ² , L ³ and L ⁴ each independently represent a single bond or a divalent linking group. A ¹ and A ² each independently represent a spacer group having 2 to 20 carbon atoms. M represents a mesogenic group.
Hereinafter, the rod-like liquid crystal compound having a reactive group represented by the general formula (I) will be described in more detail. In the formula, Q ¹ and Q ² are each independently a reactive group. The polymerization reaction of the reactive group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the reactive group is preferably a reactive group capable of addition polymerization reaction or condensation polymerization reaction. Examples of reactive groups are shown below.

Examples of the divalent linking group represented by L ¹ , L ² , L ³ and L ⁴ include —O—, —S—, —CO—, —NR ² —, —CO—O—, and —O—CO. —O—, —CO—NR ² —, —NR ² —CO—, —O—CO—, —O—CO—NR ² —, —NR ² —CO—O—, and NR ² —CO—NR ^2. A divalent linking group selected from the group consisting of-is preferred. R ² is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. In the formula (I), Q ¹ -L ¹ and Q ² -L ² -are CH ₂ ═CH—CO—O—, CH ₂ ═C (CH ₃ ) —CO—O—, and CH ₂ ═C ( Cl) -CO-O-CO- O- are _{preferable, CH 2 = CH-CO-} O- is most preferable.

A ¹ and A ² represent spacer groups having 2 to 20 carbon atoms. An alkylene group having 2 to 12 carbon atoms, an alkenylene group, and an alkynylene group are preferable, and an alkylene group is particularly preferable. The spacer group is preferably a chain and may contain oxygen atoms or sulfur atoms that are not adjacent to each other. The spacer group may have a substituent and may be substituted with a halogen atom (fluorine, chlorine, bromine), a cyano group, a methyl group, or an ethyl group.
Examples of the mesogenic group represented by M include all known mesogenic groups. In particular, a group represented by the following general formula (II) is preferable.
Formula (II): - (- W 1 -L 5) n -W 2 -
In the formula, W ¹ and W ² each independently represent a divalent cyclic alkylene group or a cyclic alkenylene group, a divalent aryl group or a divalent heterocyclic group, and L ⁵ represents a single bond or a linking group. Specific examples of the linking group include specific examples of groups represented by L ^{1 to} L ⁴ in the formula (I), —CH ₂ —O—, and —O—CH ₂ —. n represents 1, 2 or 3.

W ¹ and W ² include 1,4-cyclohexanediyl, 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5diyl, 1,3,4-thiadiazole-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,5-diyl, thiophene-2,5-diyl, pyridazine-3,6-diyl . In the case of 1,4-cyclohexanediyl, there are trans isomers and cis isomers, but either isomer may be used, and a mixture in any proportion may be used. More preferably, it is a trans form. W ¹ and W ² may each have a substituent. Examples of the substituent include a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, etc.), and an alkoxy group having 1 to 10 carbon atoms. (Methoxy group, ethoxy group, etc.), C1-10 acyl group (formyl group, acetyl group, etc.), C1-10 alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), carbon atom Examples thereof include an acyloxy group of 1 to 10 (acetyloxy group, propionyloxy group, etc.), nitro group, trifluoromethyl group, difluoromethyl group and the like.
Preferred examples of the basic skeleton of the mesogenic group represented by the general formula (II) are shown below. These may be substituted with the above substituents.

  Examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto. In addition, the compound represented by general formula (I) is compoundable by the method as described in Japanese National Patent Publication No. 11-513019 (WO97 / 00600).

  As another aspect of the present invention, there is an aspect in which a discotic liquid crystal is used for the optically anisotropic layer. The optically anisotropic layer is preferably a layer of a low molecular weight liquid crystal discotic compound such as a monomer or a polymer layer obtained by polymerization (curing) of a polymerizable liquid crystal discotic compound. Examples of the discotic (discotic) compound include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 141 (1985), Physicslett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. , 1794 (1985), J. Am. Zhang et al., J. Am. Chem. Soc. 116, page 2655 (1994), and azacrown-based and phenylacetylene-based macrocycles. The above discotic (discotic) compounds generally have a discotic nucleus at the center of the molecule, and groups (L) such as linear alkyl groups, alkoxy groups, and substituted benzoyloxy groups are substituted in a radial pattern. In other words, it has liquid crystallinity and generally includes a so-called discotic liquid crystal. However, when such an aggregate of molecules is uniformly oriented, it exhibits negative uniaxiality, but is not limited to this description. Further, in the present invention, it is not necessary that the final product is formed from a discotic compound, for example, the low molecular discotic liquid crystal has a group that reacts with heat, light, or the like. As a result, it may be polymerized or cross-linked by reaction with heat, light or the like, resulting in high molecular weight and loss of liquid crystallinity.

In the present invention, it is preferable to use a discotic liquid crystalline compound represented by the following general formula (III).
Formula (III): D (-LP) _n
In the formula, D is a discotic core, L is a divalent linking group, P is a polymerizable group, and n is an integer of 4 to 12.
In the formula (III), preferred specific examples of the discotic core (D), the divalent linking group (L) and the polymerizable group (P) are (D1) described in JP-A No. 2001-4837, respectively. To (D15), (L1) to (L25), (P1) to (P18), and the disk-shaped core (D), divalent linking group (L) and polymerizable group ( The contents regarding P) can be preferably applied here.
Preferred examples of the discotic compound are shown below.

The optically anisotropic layer is formed by applying a composition containing a liquid crystal compound (for example, a coating solution) to the surface of an alignment layer described later to obtain an alignment state exhibiting a desired liquid crystal phase, and then changing the alignment state to heat or A layer prepared by fixing by irradiation with ionizing radiation is preferred.
When a discotic liquid crystalline compound having a reactive group is used as the liquid crystalline compound, it may be fixed in any alignment state of horizontal alignment, vertical alignment, inclined alignment, and twist alignment. In the present specification, “horizontal alignment” means that in the case of a rod-like liquid crystal, the molecular long axis and the horizontal plane of the transparent support are parallel, and in the case of a disc-like liquid crystal, the circle of the core of the disc-like liquid crystal compound. The horizontal plane of the board and the transparent support is said to be parallel, but it is not required to be strictly parallel. In the present specification, an orientation with an inclination angle of less than 10 degrees with the horizontal plane is meant. And The inclination angle is preferably 0 to 5 degrees, more preferably 0 to 3 degrees, further preferably 0 to 2 degrees, and most preferably 0 to 1 degree.

  When two or more optically anisotropic layers comprising a composition containing a liquid crystalline compound are laminated, the combination of the liquid crystalline compounds is not particularly limited, and a laminate of all layers made of a discotic liquid crystalline compound, all having rod-like properties. It may be a laminate of a layer made of a liquid crystal compound, a laminate of a layer made of a composition containing a discotic liquid crystal compound and a layer made of a composition containing a rod-like liquid crystal compound. The combination of the alignment states of the layers is not particularly limited, and optically anisotropic layers having the same alignment state may be stacked, or optically anisotropic layers having different alignment states may be stacked.

  The optically anisotropic layer is preferably formed by applying a coating liquid containing a liquid crystalline compound and the following polymerization initiator and other additives onto a predetermined alignment layer described later. As the solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

[Fixation of alignment state of liquid crystalline compounds]
The aligned liquid crystalline compound is preferably fixed while maintaining the alignment state. The immobilization is preferably carried out by a polymerization reaction of a reactive group introduced into the liquid crystal compound. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator, and a photopolymerization reaction is more preferable. The photopolymerization reaction may be either radical polymerization or cationic polymerization. Examples of radical photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics. Aciloin compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,212,970). Examples of the cationic photopolymerization initiator include organic sulfonium salt systems, iodonium salt systems, phosphonium salt systems, and the like. Organic sulfonium salt systems are preferable, and triphenylsulfonium salts are particularly preferable. As counter ions of these compounds, hexafluoroantimonate, hexafluorophosphate, and the like are preferably used.

It is preferable that the usage-amount of a photoinitiator is 0.01-20 mass% of solid content of a coating liquid, and it is further more preferable that it is 0.5-5 mass%. Light irradiation for the polymerization of the liquid crystalline compound is preferably performed using ultraviolet rays. Irradiation energy is preferably ^{10mJ / cm 2 ~10J / cm 2} , further preferably 25~800mJ / cm ^2. Illuminance is preferably 10 to 1,000 / cm ^2, more preferably 20 to 500 mW / cm ^2, further preferably 40~350mW / cm ^2. The irradiation wavelength preferably has a peak at 250 to 450 nm, and more preferably has a peak at 300 to 410 nm. In order to accelerate the photopolymerization reaction, light irradiation may be performed under an inert gas atmosphere such as nitrogen or under heating conditions.

[Optical alignment by polarized irradiation]
The optically anisotropic layer may be a layer that exhibits or increases in-plane retardation by photo-alignment by polarized light irradiation. This polarized light irradiation may serve as the photopolymerization process in the above-described orientation fixing, or may be further fixed by non-polarized light irradiation after first polarized light irradiation, or may be fixed first by non-polarized light irradiation. The photo-alignment may be carried out by irradiation with polarized light, but it is desirable to carry out only the irradiation with polarized light or to perform further immobilization with non-polarized light after performing polarized light irradiation first. When polarized light irradiation also serves as a photopolymerization process in the above-described orientation fixation and a radical polymerization initiator is used as a polymerization initiator, polarized light irradiation should be performed in an inert gas atmosphere with an oxygen concentration of 0.5% or less. preferable. The irradiation energy is preferably ^{20mJ / cm 2 ~10J / cm 2} , further preferably 100 to 800 mJ / cm ^2. The illuminance is preferably 20 to 1000 mW / cm ^2, more preferably 50 to 500 mW / cm ^2, further preferably 100 to 350 mW / cm ^2. Although there is no restriction | limiting in particular about the kind of liquid crystalline compound hardened | cured by polarized light irradiation, The liquid crystalline compound which has an ethylenically unsaturated group as a reactive group is preferable. The irradiation wavelength preferably has a peak at 300 to 450 nm, and more preferably has a peak at 350 to 400 nm.

[Post-curing by UV irradiation after polarized irradiation]
The optically anisotropic layer may be further irradiated with polarized or non-polarized ultraviolet rays after the first irradiation with polarized light (irradiation for photo-alignment). By further irradiating polarized or non-polarized ultraviolet rays after the first irradiation with polarized light, the reaction rate of the reactive group is increased (post-curing), the adhesiveness and the like are improved, and production can be carried out at a high transport speed. Post-curing may be polarized or non-polarized, but is preferably polarized. Moreover, it is preferable to carry out post-curing twice or more, and polarized light or non-polarized light may be combined with polarized light and non-polarized light. However, when combined, it is preferable to irradiate polarized light before non-polarized light. Irradiation with ultraviolet rays may or may not be replaced with an inert gas. However, particularly when a radical polymerization initiator is used as the polymerization initiator, it is preferably performed in an inert gas atmosphere having an oxygen concentration of 0.5% or less. The irradiation energy is preferably ^{20mJ / cm 2 ~10J / cm 2} , further preferably 100 to 800 mJ / cm ^2. The illuminance is preferably 20 to 1000 mW / cm ^2, more preferably 50 to 500 mW / cm ^2, further preferably 100 to 350 mW / cm ^2. In the case of polarized light irradiation, the irradiation wavelength preferably has a peak at 300 to 450 nm, and more preferably 350 to 400 nm. In the case of non-polarized light irradiation, it preferably has a peak at 200 to 450 nm, and more preferably has a peak at 250 to 400 nm.

[Fixing of alignment state of liquid crystal compound having radical reactive group and cationic reactive group]
As described above, it is also preferable that the liquid crystalline compound has two or more kinds of reactive groups having different polymerization conditions. In this case, it is possible to produce an optically anisotropic layer including a polymer having an unreacted reactive group by selecting conditions and polymerizing only a part of plural types of reactive groups. . Polymerization particularly suitable when such a liquid crystalline compound is a liquid crystalline compound having a radical reactive group and a cationic reactive group (specific examples are, for example, the aforementioned I-22 to I-25). The immobilization conditions will be described below.

  First, as the polymerization initiator, it is preferable to use only a photopolymerization initiator that acts on a reactive group intended to be polymerized. That is, it is preferable to use only a radical photopolymerization initiator when selectively polymerizing radical reactive groups and only a cationic photopolymerization initiator when selectively polymerizing cationic reactive groups. The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.1 to 8% by mass, and 0.5 to 4% by mass of the solid content of the coating solution. It is particularly preferred.

Next, it is preferable to use ultraviolet rays for light irradiation for polymerization. At this time, if the irradiation energy and / or illuminance is too strong, both the radical reactive group and the cationic reactive group may react non-selectively. Accordingly, the irradiation energy is preferably ^{5mJ / cm 2 ~500mJ / cm 2} , more preferably 10 to 400 mJ / cm ^2, and particularly preferably ^{20mJ / cm 2 ~200mJ / cm 2} . The illuminance is preferably 5 to 500 mW / cm ^2, more preferably 10 to 300 mW / cm ^2, and particularly preferably 20 to 100 mW / cm ^2. The irradiation wavelength preferably has a peak at 250 to 450 nm, and more preferably has a peak at 300 to 410 nm.

  Of the photopolymerization reactions, reactions using radical photopolymerization initiators are inhibited by oxygen, and reactions using cationic photopolymerization initiators are not inhibited by oxygen. Therefore, when a liquid crystal compound having a radical reactive group and a cationic reactive group is used as the liquid crystalline compound and one kind of the reactive group is selectively polymerized, the radical reactive group is selectively polymerized. In some cases, it is preferable to perform light irradiation in an inert gas atmosphere such as nitrogen, and in the case of selectively polymerizing a cationic reactive group, light irradiation is performed under an oxygen-containing atmosphere (for example, in the air). It is preferable.

[Horizontal alignment agent]
In the composition for forming an optically anisotropic layer, at least one of a fluorine-containing homopolymer or copolymer using a compound represented by the following general formulas (1) to (3) and a monomer represented by the general formula (4): By containing, the molecules of the liquid crystal compound can be substantially horizontally aligned.
Hereinafter, the following general formulas (1) to (4) will be described in order.

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and X ¹ , X ² and X ^{3 each} represent a single bond or a divalent linking group. The substituent represented by each of R ^{1 to} R ³ is preferably a substituted or unsubstituted alkyl group (more preferably an unsubstituted alkyl group or a fluorine-substituted alkyl group), an aryl group (particularly a fluorine-substituted alkyl). An aryl group having a group is preferred), a substituted or unsubstituted amino group, an alkoxy group, an alkylthio group, and a halogen atom. The divalent linking groups represented by X ¹ , X ² and X ³ are each an alkylene group, an alkenylene group, a divalent aromatic group, a divalent heterocyclic residue, —CO—, —NR ^a — ( R ^a is ^a divalent linking group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), —O—, —S—, —SO—, —SO ₂ —, and combinations thereof. Preferably there is. The divalent linking group is selected from the group consisting of an alkylene group, a phenylene group, —CO—, —NR ^a —, —O—, —S—, and SO ₂ —, or the group. It is more preferably a divalent linking group in which at least two groups are combined. The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The number of carbon atoms of the divalent aromatic group is preferably 6-10.

In the formula, R represents a substituent, and m represents an integer of 0 to 5. When m represents an integer greater than or equal to 2, several R may be same or different. Preferred substituents for R are the same as those listed as preferred ranges for the substituents represented by R ¹ , R ² , and R ³ . m preferably represents an integer of 1 to 3, particularly preferably 2 or 3.

In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a substituent. The substituents represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are preferably the substituents represented by R ¹ , R ² and R ³ in the general formula (1). It is listed as a thing. As the horizontal alignment agent used in the present invention, the compounds described in paragraphs [0092] to [0096] of JP-A-2005-99248 can be used, and the synthesis method of these compounds is also described in the specification. ing.

In the formula, R represents a hydrogen atom or a methyl group, X represents an oxygen atom or a sulfur atom, Z represents a hydrogen atom or a fluorine atom, m is an integer of 1 to 6, and n is an integer of 1 to 12. Represents. In addition to the fluorine-containing polymer containing the general formula (4), the compounds described in JP-A-2005-206638 and JP-A-2006-91205 can be used as the unevenness improving polymer in coating as a horizontal alignment agent. Are also described in the specification.
The addition amount of the horizontal alignment agent is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.02 to 1% by mass of the mass of the liquid crystal compound. In addition, the compounds represented by the general formulas (1) to (4) may be used alone or in combination of two or more.

[Optically anisotropic layer produced by stretching]
The optically anisotropic layer may be prepared by stretching a polymer. As described above, the optically anisotropic layer preferably has at least one unreacted reactive group. However, when preparing such a polymer, the polymer having a reactive group may be stretched in advance. Alternatively, a reactive group may be introduced into the optically anisotropic layer after stretching using a coupling agent or the like. Features of the optically anisotropic layer obtained by the stretching method include low cost and self-supporting property (no support is required for forming and maintaining the optically anisotropic layer).

[Post-treatment of optically anisotropic layer]
Various post-treatments may be performed in order to modify the produced optically anisotropic layer. Examples of post-treatment include corona treatment for improving adhesion, addition of a plasticizer for improving flexibility, addition of a thermal polymerization inhibitor for improving storage stability, and a coupling treatment for improving reactivity. It is done. Further, when the polymer in the optically anisotropic layer has an unreacted reactive group, addition of a polymerization initiator corresponding to the reactive group is also an effective modifying means. For example, adding a radical photopolymerization initiator to an optically anisotropic layer obtained by polymerizing and fixing a liquid crystalline compound having a cationic reactive group and a radical reactive group using a cationic photopolymerization initiator Thus, the reaction of an unreacted radical reactive group when pattern exposure is performed later can be promoted. Examples of the means for adding the plasticizer and the photopolymerization initiator include a means for immersing the optically anisotropic layer in a solution of the corresponding additive and a solution of the corresponding additive on the optically anisotropic layer. And means for infiltration. In addition, when another layer is applied on the optically anisotropic layer, an additive may be added to the coating solution of the layer and immersed in the optically anisotropic layer.

[Birefringence pattern builder]
The birefringence pattern builder is a material for producing a birefringence pattern, and a material capable of obtaining a birefringence pattern through a predetermined process. The birefringence pattern builder may be usually a film or a sheet. In addition to the optically anisotropic layer described above, the birefringence pattern builder may have a functional layer capable of imparting various secondary functions. Examples of the functional layer include a support, an alignment layer, a reflective layer, and a back adhesive layer. In addition, a birefringence pattern builder used as a transfer material or a birefringence pattern builder made using a transfer material may have a temporary support, a transfer adhesive layer, or a mechanical property control layer. Good.

[Support]
The birefringence pattern builder may have a support for the purpose of maintaining mechanical stability. The support used for the birefringence pattern builder is not particularly limited, and may be rigid or flexible. The rigid support is not particularly limited, but is a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, a metal such as an aluminum plate, an iron plate, or a SUS plate. A board, a resin board, a ceramic board, a stone board, etc. are mentioned. There are no particular limitations on the flexible support, but cellulose esters (eg, cellulose acetate, cellulose propionate, cellulose butyrate), polyolefins (eg, norbornene polymers), poly (meth) acrylic acid esters (eg, polymethyl) Methacrylate), polycarbonate, polyester and polysulfone, norbornene polymers and other plastic films, paper, aluminum foil, cloth and the like. In view of ease of handling, the thickness of the rigid support is preferably 100 to 3000 μm, and more preferably 300 to 1500 μm. As a film thickness of a flexible support body, 3-500 micrometers is preferable and 10-200 micrometers is more preferable. The support preferably has heat resistance sufficient not to be colored or deformed by baking to be described later. It is also preferable that the support itself has a reflecting function instead of the reflecting layer described later.
When the support is a substrate for a liquid crystal display substrate, the support is preferably transparent. The substrate for the liquid crystal display device substrate may be a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, or a transparent substrate made of a polymer. In the case of a liquid crystal display device, it is preferable to have heat resistance because a high temperature process of 180 ° C. or higher is required in order to bake the color filter and the alignment film in the liquid crystal display device substrate manufacturing process. As such a heat-resistant substrate, a glass plate or polyimide, polyethersulfone, heat-resistant polycarbonate, or polyethylene naphthalate is preferable, and a glass plate is particularly preferable from the viewpoint of price, transparency, and heat resistance. In addition, the substrate can be made to adhere well to the transfer adhesive layer by performing a coupling treatment in advance. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. Although not particularly limited, the film thickness of the substrate is generally preferably 100 to 1200 μm, particularly preferably 300 to 1000 μm.
The substrate used for manufacturing the substrate for a liquid crystal display device of the present invention may be a color filter substrate having a color filter layer on the glass substrate.

[Alignment layer]
As described above, an alignment layer may be used for forming the optically anisotropic layer. The alignment layer is generally provided on a support or temporary support or an undercoat layer coated on the support or temporary support. The alignment layer functions so as to define the alignment direction of the liquid crystal compound provided thereon. The orientation layer may be any layer as long as it can impart orientation to the optically anisotropic layer. Preferred examples of the alignment layer include a rubbing treatment layer of an organic compound (preferably a polymer), an oblique deposition layer of an inorganic compound, and a layer having a microgroove, and ω-tricosanoic acid, dioctadecylmethylammonium chloride and stearyl. Examples include a cumulative film formed by Langmuir-Blodgett method (LB film) such as methyl acid, or a layer in which a dielectric is oriented by applying an electric field or a magnetic field.

  Examples of organic compounds for the alignment layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleimide copolymer, polyvinyl alcohol, poly (N-methylolacrylamide), polyvinylpyrrolidone, styrene / vinyltoluene. Copolymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, carboxymethyl cellulose, polyethylene, polypropylene, polycarbonate, etc. And polymers such as silane coupling agents. Examples of preferable polymers include polyimide, polystyrene, polymers of styrene derivatives, gelatin, polyvinyl alcohol, and alkyl-modified polyvinyl alcohol having an alkyl group (preferably having 6 or more carbon atoms).

  A polymer is preferably used for forming the alignment layer. The type of polymer that can be used can be determined according to the orientation (particularly the average tilt angle) of the liquid crystal compound. For example, in order to align the liquid crystalline compound horizontally, a polymer that does not decrease the surface energy of the alignment layer (ordinary alignment polymer) is used. Specific types of polymers are described in various documents about liquid crystal cells or optical compensation sheets. For example, polyvinyl alcohol or modified polyvinyl alcohol, a copolymer with polyacrylic acid or polyacrylate, polyvinyl pyrrolidone, cellulose, or modified cellulose are preferably used. The alignment layer material may have a functional group capable of reacting with the reactive group of the liquid crystal compound. The reactive group can be introduced by introducing a repeating unit having a reactive group in the side chain or as a substituent of a cyclic group. It is more preferable to use an alignment layer that forms a chemical bond with the liquid crystal compound at the interface. Such an alignment layer is described in JP-A-9-152509, and acid chloride or Karenz MOI (manufactured by Showa Denko KK). The modified polyvinyl alcohol in which an acrylic group is introduced into the side chain by using The thickness of the alignment layer is preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm. The alignment layer may have a function as an oxygen blocking film.

  A polyimide film (preferably fluorine atom-containing polyimide) widely used as an alignment layer for LCD is also preferable as the organic alignment layer. This is a polyamic acid (for example, LQ / LX series manufactured by Hitachi Chemical Co., Ltd., SE series manufactured by Nissan Chemical Co., Ltd., etc.) is applied to the support surface and baked at 100 to 300 ° C. for 0.5 to 1 hour. And then obtained by rubbing.

  Moreover, the rubbing process can utilize a processing method widely adopted as a liquid crystal alignment process of LCD. That is, a method of obtaining the orientation by rubbing the surface of the orientation layer in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. Generally, it is carried out by rubbing several times using a cloth or the like in which fibers having a uniform length and thickness are planted on average.

Moreover, as a vapor deposition material for the inorganic oblique vapor deposition film, SiO ₂ is representative, and metal oxides such as TiO ₂ and ZnO ₂ , fluorides such as MgF ₂ , and metals such as Au and Al. The metal oxide can be used as an oblique deposition material as long as it has a high dielectric constant, and is not limited to the above. The inorganic oblique deposition film can be formed using a deposition apparatus. An inorganic oblique vapor deposition film can be formed by fixing the film (support) and performing vapor deposition, or moving the long film and performing continuous vapor deposition.

[Reflective layer]
The birefringence pattern builder may have a reflective layer for producing a birefringence pattern that can be more easily identified. Although it does not specifically limit as a reflection layer, For example, metal layers, such as aluminum and silver, are mentioned.

[Rear adhesive layer]
The birefringence pattern builder may have a post-adhesive layer for attaching an article having a birefringence pattern produced after pattern exposure and baking described later to another article. The material of the post-adhesion layer is not particularly limited, but is preferably a material having adhesiveness even after undergoing a baking process for producing a birefringence pattern.

[Two or more optically anisotropic layers]
The birefringence pattern builder may have two or more optically anisotropic layers. Two or more optically anisotropic layers may be adjacent to each other in the normal direction, or another functional layer may be sandwiched therebetween. Two or more optically anisotropic layers may have almost the same retardation or different retardations. Further, the slow axis directions may be in substantially the same direction, or may be in different directions.

An example of using a birefringence pattern builder having two or more optically anisotropic layers laminated so that the slow axes face the same direction is the case of producing a pattern having a large retardation. A patterned optically anisotropic layer containing a region having a large retardation by laminating with two or three layers and then pattern exposure even if the required optically anisotropic layer is insufficient for one layer. Can be easily obtained.
An example of using a birefringence pattern builder having two or more optically anisotropic layers having different retardations and slow axes is the case of producing a patterned broadband λ / 4 plate. As a method of creating a broadband λ / 4 plate, a method of laminating a λ / 4 plate and a λ / 2 plate with their slow axes shifted by 60 ° has been announced (Research Report of Ono et al., IDW 2005.1411). In order to fabricate such a broadband λ / 4 plate pattern, a birefringence pattern builder having a λ / 4 plate and a λ / 2 plate laminated with their slow axes shifted by 60 ° is useful.

[Photosensitive resin layer]
The photosensitive resin layer functions as a transfer adhesive layer in a transfer material described later or as a layer for forming a step in a liquid crystal display device.
The photosensitive resin layer is made of a photosensitive resin composition, and may be positive or negative and is not particularly limited, and a commercially available resist material can also be used. When used as a transfer adhesive layer, it is preferable to exhibit adhesiveness by light irradiation. In view of environmental and explosion-proof problems in the manufacturing process of articles such as substrates for liquid crystal display devices, aqueous development with an organic solvent of 5% or less is preferred, and alkaline development is particularly preferred. The photosensitive resin layer is preferably formed from a resin composition containing at least (1) a polymer, (2) a monomer or oligomer, and (3) a photopolymerization initiator or a photopolymerization initiator system.

Hereinafter, the components (1) to (3) will be described.
(1) Polymer As the polymer (hereinafter sometimes simply referred to as “binder”), an alkali-soluble resin composed of a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Further, as particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid and other monomers And a multi-component copolymer. These binder polymers having polar groups may be used alone or in the form of a composition used in combination with ordinary film-forming polymers. The polymer content relative to the total solid content is generally 20 to 70% by mass, preferably 25 to 65% by mass, and more preferably 25 to 45% by mass.

(2) Monomer or oligomer The monomer or oligomer used in the photosensitive resin layer is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization by light irradiation. . Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexa Diol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.
Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in JP-B-52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.
These monomers or oligomers may be used alone or in admixture of two or more. The content of the colored resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred.

(3) Photopolymerization initiator or photopolymerization initiator system As the photopolymerization initiator or photopolymerization initiator system used in the photosensitive resin layer, a vicinal poly disclosed in US Pat. No. 2,367,660 is used. Ketaldonyl compounds, acyloin ether compounds described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Pat. No. 3,046,127 And a polynuclear quinone compound described in U.S. Pat. No. 2,951,758, a combination of a triarylimidazole dimer described in U.S. Pat. No. 3,549,367 and a p-aminoketone, and a benzoin described in JP-B 51-48516. Thiazole compounds and trihalomethyl-s-triazine compounds, US Pat. No. 4,239,850 It may be mentioned triazine compounds, U.S. Patent trihalomethyl oxadiazole compounds described in No. 4,212,976 specification or the like - trihalomethyl listed in. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.
In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.

These photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or the photopolymerization initiator system with respect to the total solid content of the colored resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

The photosensitive resin layer preferably contains an appropriate surfactant from the viewpoint of effectively preventing unevenness. The surfactant can be used as long as it is mixed with the photosensitive resin composition. Preferred surfactants used in the present invention include JP 2003-337424 A [0090] to [0091], JP 2003-177522 A [0092] to [0093], and JP 2003-177523 A [0094]. ] To [0095], JP 2003-177521 A [0096] to [0097], JP 2003-177519 A [0098] to [0099], JP 2003-177520 A [0100] to [0101]. [0102] to [0103] of JP-A-11-133600 and surfactants disclosed as inventions of JP-A-6-16684 are preferred. In order to obtain a higher effect, a fluorosurfactant and / or a silicon surfactant (a fluorosurfactant or a silicon surfactant, a surfactant containing both a fluorine atom and a silicon atom) ) Or two or more types are preferable, and a fluorosurfactant is most preferable. When using a fluorosurfactant, the number of fluorine atoms in the fluorine-containing substituent in the surfactant molecule is preferably 1 to 38, more preferably 5 to 25, and most preferably 7 to 20. If the number of fluorine atoms is too large, it is not preferable in that the solubility in an ordinary solvent containing no fluorine is lowered. If the number of fluorine atoms is too small, it is not preferable in that the effect of improving unevenness cannot be obtained.
As a particularly preferred surfactant, the following general formula (a) and a monomer represented by the general formula (b) are included, and the mass ratio of the general formula (a) / the general formula (b) is 20/80 to 60 / The thing containing 40 copolymers is mentioned.

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 to 18, and m represents an integer of 2 to 14. p and q represent integers of 0 to 18, but are not included when both p and q are simultaneously 0.

A particularly preferred surfactant represented by the general formula (a) is referred to as a monomer (a), and a monomer represented by the general formula (b) is referred to as a monomer (b). C _m F _{2m + 1} shown in the general formula (a) may be linear or branched. m shows the integer of 2-14, Preferably it is an integer of 4-12. The content of C _m F _{2m + 1} is preferably 20 to 70% by mass, particularly preferably 40 to 60% by mass, based on the monomer (a). R ¹ represents a hydrogen atom or a methyl group. Moreover, n shows 1-18, and 2-10 are preferable especially. R ² and R ³ shown in the general formula (b) each independently represent a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p and q each represent an integer of 0 to 18, but p and q do not include 0. p and q are preferably 2 to 8.

Moreover, as a particularly preferable monomer (a) contained in one molecule of the surfactant, those having the same structure or different structures within the above defined range may be used. The same applies to the monomer (b).
The particularly preferable weight average molecular weight Mw of the surfactant is preferably 1000 to 40000, and more preferably 5000 to 20000. The surfactant contains the monomer represented by the general formula (a) and the general formula (b), and the weight ratio of the general formula (a) / the general formula (b) is 20/80 to 60/40. It is characterized by containing a coalescence. Particularly preferred 100 parts by weight of the surfactant is preferably such that the monomer (a) is 20 to 60 parts by weight, the monomer (b) is 80 to 40 parts by weight, and other optional monomers are the remaining parts by weight. It is preferable that the monomer (a) is composed of 25 to 60 parts by mass, the monomer (b) is composed of 60 to 40 parts by mass, and other optional monomers are composed of the remaining part by mass.

Examples of copolymerizable monomers other than the monomers (a) and (b) include styrene, vinyl toluene, α-methyl styrene, 2-methyl styrene, chlorostyrene, vinyl benzoic acid, sodium vinylbenzene sulfonate, aminostyrene, and the like. Styrene and its derivatives, substituted products, dienes such as butadiene and isoprene, acrylonitrile, vinyl ethers, methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, partially esterified maleic acid, styrene sulfonic acid maleic anhydride, silica And vinyl monomers such as cinnamate, vinyl chloride and vinyl acetate.
Particularly preferred surfactants are copolymers such as monomer (a) and monomer (b), but the monomer sequence is not particularly limited and may be random or regular, for example, block or graft. Furthermore, particularly preferable surfactants can be used by mixing two or more of those having different molecular structures and / or monomer compositions.
As content of the said surfactant, 0.01-10 mass% is preferable with respect to the layer total solid of a photosensitive resin layer, and 0.1-7 mass% is especially preferable. The surfactant contains a predetermined amount of a surfactant having a specific structure, an ethylene oxide group, and a polypropylene oxide group, and a liquid crystal provided with the photosensitive resin layer by containing it in a specific range in the photosensitive resin layer. Display unevenness of the display device is improved. If it is less than 0.01% by mass relative to the total solid content, the display unevenness is not improved, and if it exceeds 10% by mass, the effect of improving the display unevenness does not appear much. When the above-mentioned particularly preferable surfactant is contained in the photosensitive resin layer to produce a color filter, it is preferable in that display unevenness is improved.

  Specific examples of preferable fluorine-based surfactants include compounds described in paragraph numbers [0054] to [0063] of JP-A No. 2004-163610. Moreover, the following commercially available surfactant can also be used as it is. Examples of commercially available surfactants that can be used include F-top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (manufactured by Sumitomo 3M Ltd.), MegaFuck F171, F173, F176, F189, and R08. (Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.) and other fluorine-based surfactants, or silicon-based surfactants. be able to. Polysiloxane polymers KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) can also be used as the silicon surfactant. In the present invention, a compound described in paragraphs [0046] to [0052] of JP-A No. 2004-331812, which is a fluorine-based surfactant not containing the monomer represented by the general formula (a), is used. Is also preferable.

[Production method of birefringence pattern builder]
The method for producing the birefringence pattern builder is not particularly limited, but for example, an optically anisotropic layer is directly formed on the support, and another birefringence pattern builder is used as a transfer material for optical on the support. Self-supporting optical anisotropy layer forming other functional layer on self-supporting optical anisotropy layer, forming an anisotropic layer as a self-supporting optical anisotropic layer And a method such as bonding to a support. Among these, from the point of not restricting the physical properties of the optically anisotropic layer, a method of directly forming the optically anisotropic layer on the support and a transfer material are used to transfer the optically anisotropic layer onto the support. A method is preferable, and a method of transferring an optically anisotropic layer onto a support using a transfer material is more preferable because there are few restrictions on the support. In the case where the article having a birefringence pattern is a substrate for a liquid crystal display device, the number of manufacturing steps having a photosensitive resin layer for forming a step can be particularly reduced by forming it using a transfer material.

As a method for producing a birefringence pattern builder comprising two or more optically anisotropic layers, another birefringence pattern builder is used as a transfer material, in which an optically anisotropic layer is directly formed on a birefringence pattern builder. And a method of transferring the optically anisotropic layer onto the birefringence pattern builder. Among these, a method of transferring an optically anisotropic layer onto a birefringence pattern builder using a birefringence pattern builder as a transfer material is more preferable.
The birefringence pattern builder used as a transfer material will be described below. Note that the birefringence pattern builder used as a transfer material may be referred to as a “birefringence pattern builder” in Examples and the like to be described later.

[Temporary support]
The birefringence pattern builder used as a transfer material preferably has a temporary support. The temporary support may be transparent or opaque and is not particularly limited. Examples of polymers constituting the temporary support include cellulose esters (eg, cellulose acetate, cellulose propionate, cellulose butyrate), polyolefins (eg, norbornene-based polymers), poly (meth) acrylic acid esters (eg, poly Methyl methacrylate), polycarbonate, polyester and polysulfone, norbornene-based polymers. For the purpose of inspecting optical properties in the production process, the transparent support is preferably a transparent and low birefringent material, and from the viewpoint of low birefringence, cellulose ester and norbornene are preferred. As a commercially available norbornene-based polymer, Arton (manufactured by JSR Co., Ltd.), Zeonex, Zeonore (manufactured by Nippon Zeon Co., Ltd.), or the like can be used. Inexpensive polycarbonate, polyethylene terephthalate, and the like are also preferably used.

[Transfer adhesive layer]
The transfer material preferably has a transfer adhesive layer. The transfer adhesive layer is not particularly limited as long as it is transparent, uncolored, and has sufficient transferability, such as a pressure-sensitive adhesive layer, a pressure-sensitive resin layer, a heat-sensitive resin layer, and the above-described photosensitive resin layer. However, a photosensitive or heat-sensitive resin layer is desirable from the viewpoint of baking resistance required when used for a liquid crystal display substrate or the like.

As the pressure-sensitive adhesive, for example, a material that is excellent in optical transparency and exhibits appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties is preferable. Specific examples include pressure-sensitive adhesives that are appropriately prepared using a polymer such as an acrylic polymer, silicone polymer, polyester, polyurethane, polyether, and synthetic rubber as a base polymer. Control of the adhesive properties of the pressure-sensitive adhesive layer can be achieved by, for example, controlling the degree of crosslinking and molecular weight depending on the composition and molecular weight of the base polymer forming the pressure-sensitive adhesive layer, the crosslinking method, the content ratio of the crosslinkable functional group, the blending ratio of the crosslinking agent, etc. It can be suitably performed by a conventionally known method such as adjustment.

  The pressure-sensitive resin layer is not particularly limited as long as adhesiveness is exhibited by applying pressure, and rubber-based, acrylic-based, vinyl ether-based, and silicone-based pressure-sensitive adhesives can be used as the pressure-sensitive adhesive. In the production stage and coating stage of adhesives, solvent-based adhesives, non-aqueous emulsion adhesives, water-based emulsion adhesives, water-soluble adhesives, hot melt adhesives, liquid curable adhesives, and delayed A tack-type adhesive can be used. The rubber-based pressure-sensitive adhesive is disclosed in New Polymer Library 13 “Adhesion Technology”, Kobunshi Publishing Co., Ltd. 41 (1987). The vinyl ether-based pressure-sensitive adhesive includes those having a main component of an alkyl vinyl ether polymer having 2 to 4 carbon atoms, vinyl chloride / vinyl acetate copolymer, vinyl acetate polymer, polyvinyl butyral and the like mixed with a plasticizer. As the silicone-based pressure-sensitive adhesive, a rubbery siloxane can be used to give film formation and film condensing power, and a resinous siloxane can be used to give adhesiveness and adhesion.

  The heat-sensitive resin layer is not particularly limited as long as it exhibits adhesiveness by applying heat, and examples of the heat-sensitive adhesive include hot-melt compounds and thermoplastic resins. Examples of the heat-meltable compound include low molecular weight products of thermoplastic resins such as polystyrene resin, acrylic resin, styrene-acrylic resin, polyester resin, and polyurethane resin, carnauba wax, molasses, candelilla wax, rice wax, and Plant waxes such as aucuric wax, beeswax, insect wax, shellac, and animal waxes such as whale wax, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, ester wax, and oxidation Examples include various waxes such as petroleum waxes such as waxes, and mineral waxes such as montan wax, ozokerite, and ceresin wax. Furthermore, rosin derivatives such as rosin, hydrogenated rosin, polymerized rosin, rosin modified glycerin, rosin modified maleic resin, rosin modified polyester resin, rosin modified phenolic resin and ester gum, phenol resin, terpene resin, ketone resin, cyclopentadiene Examples thereof include resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, and alicyclic hydrocarbon resins.

  These heat-meltable compounds preferably have a molecular weight of usually 10,000 or less, particularly 5,000 or less and a melting point or softening point in the range of 50 to 150 ° C. These hot melt compounds may be used alone or in combination of two or more. Examples of the thermoplastic resin include ethylene copolymers, polyamide resins, polyester resins, polyurethane resins, polyolefin resins, acrylic resins, and cellulose resins. Of these, ethylene copolymers and the like are particularly preferably used.

[Mechanical property control layer]
It is preferable to form a mechanical property control layer between the temporary support and the optically anisotropic layer of the transfer material in order to control the mechanical properties and the uneven followability. As the mechanical property control layer, those exhibiting flexible elasticity, those softened by heat, those exhibiting fluidity by heat, and the like are preferable, and a thermoplastic resin layer is particularly preferable. As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxy Chill nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

[Peeling layer]
The birefringence pattern builder used as the transfer material may have a release layer on the temporary support. The release layer controls the adhesion between the temporary support and the release layer, or between the release layer and the layer immediately above it, and has a role of assisting the release of the temporary support after transferring the optically anisotropic layer. In addition, the other functional layers described above, such as an alignment layer and a mechanical property control layer, may have a function as a release layer.
In the transfer material, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen barrier film having an oxygen barrier function described in JP-A-5-72724 as an “isolation layer” or the alignment layer for forming the optical anisotropy. Of these, a layer formed by mixing polyvinyl alcohol or polyvinylpyrrolidone and one or more of these modified products is particularly preferable. The thermoplastic resin layer, the oxygen blocking film, and the alignment layer can also be used.

[Surface protective layer]
A thin surface protective layer is preferably provided on the resin layer in order to protect it from contamination and damage during storage. The nature of the surface protective layer is not particularly limited and may be made of the same or similar material as the temporary support, but it must be easily separated from the adjacent layer (for example, transfer adhesive layer). As a material for the surface protective layer, for example, silicon paper, polyolefin or polytetrafluoroethylene sheet is suitable.

Each layer such as optically anisotropic layer, photosensitive resin layer, transfer adhesive layer and orientation layer formed as desired, thermoplastic resin layer, mechanical property control layer and intermediate layer is formed by dip coating, air knife coating, spin It can be formed by coating by a coating method, slit coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method or extrusion coating method (US Pat. No. 2,681,294). Two or more layers may be applied simultaneously. The methods for simultaneous application are described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).
In addition, when applying a layer (for example, a transfer adhesive layer) to be applied on the optically anisotropic layer, by adding a plasticizer or a photopolymerization initiator to the coating solution, the optical by immersion of these additives is added. The anisotropic layer may be modified at the same time.

[Method of transferring transfer material onto transfer material]
The method for transferring the transfer material onto a transfer material such as a support (substrate) is not particularly limited, and the method is not particularly limited as long as the optically anisotropic layer can be transferred onto the substrate. For example, a transfer material formed in a film shape can be attached by pressing or thermocompression bonding with a roller or flat plate heated and / or pressurized using a laminator with the transfer adhesive layer surface side of the transfer material surface side. . Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575.
Examples of the material to be transferred include a support, a laminate including a support and another functional layer, or a birefringence pattern builder.

[Transfer process]
After transferring the birefringence pattern transfer material onto the transfer material, the temporary support may or may not be peeled off. However, when it does not peel, it is preferable that the temporary support has transparency suitable for subsequent pattern exposure, heat resistance that can withstand baking, and the like. Further, there may be a step of removing unnecessary layers transferred together with the optically anisotropic layer. For example, when a copolymer of polyvinyl alcohol and polyvinyl pyrrolidone is used as the alignment layer, the layer above the alignment layer can be removed by development with a weak alkaline aqueous developer. As a development method, a known method such as paddle development, shower development, shower & spin development, dip development or the like can be used. The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

  Further, after transfer, another layer such as an electrode layer may be formed on the surface after the temporary support is peeled off or the unnecessary layer is removed as necessary. Alternatively, the transfer material may be transferred to the surface after the temporary support is removed or the unnecessary layer is removed as necessary. The transfer material used at this time may be the same as or different from the transfer material previously transferred. Further, the slow axis of the optically anisotropic layer of the transfer material previously transferred and the optically anisotropic layer and slow axis of the newly transferred transfer material may be in the same direction or in different directions. As described above, transferring a plurality of optically anisotropic layers means that a birefringence pattern having a large retardation and a slow axis having a large retardation formed by laminating a plurality of optically anisotropic layers having the same slow axis direction. This is useful for producing a special birefringence pattern in which a plurality of layers having different directions are laminated.

[Production of an article having a birefringence pattern]
By performing at least pattern exposure and heating (baking) in this order on the birefringence pattern builder, an article having a birefringence pattern can be produced.

[Pattern exposure]
Pattern exposure for producing a birefringence pattern is performed so as to expose a region where birefringence is to be left in the birefringence pattern builder. The retardation disappearance temperature rises in the optically anisotropic layer in the exposed area. As a pattern exposure method, contact exposure using a mask, proxy exposure, projection exposure, or the like may be used, or direct drawing may be performed by focusing on a predetermined position without using a mask using a laser or an electron beam. The irradiation wavelength of the light source for the exposure preferably has a peak at 250 to 450 nm, and more preferably has a peak at 300 to 410 nm. In the case where a step is simultaneously formed by the photosensitive resin layer, it is also preferable to irradiate light in a wavelength region that can cure the resin layer (eg, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a blue laser, and the like can be given. Usually 3~2000mJ / cm ² about the preferred amount of exposure, and more preferably 5~1000mJ / cm ² or so, more preferably 10 to 500 mJ / cm ² or so, and most preferably at about 10 to 100 mJ / cm ² .

  A new birefringence pattern transfer material may be transferred onto a laminate obtained by pattern exposure of the birefringence pattern builder, and then a new pattern exposure may be performed. In this case, the first and second unexposed areas (normally the lowest retardation value), the first exposed area and the second unexposed area, and the first and second time. The retardation value remaining after baking can be effectively changed in an area that is an exposed area (usually the highest retardation value). It should be noted that the region that is the unexposed portion at the first time and the exposed portion at the second time is considered to be the same as the region that is the exposed portion at the first time and the second time by the second exposure. Similarly, four or more regions can be easily formed by alternately performing transfer and pattern exposure three times and four times.

[Heating (Bake)]
A birefringence pattern can be prepared by heating the birefringence pattern builder subjected to pattern exposure to 50 ° C. or higher and 400 ° C. or lower, preferably 80 ° C. or higher and 400 ° C. or lower. When the retardation disappearance temperature before exposure of the optical anisotropic layer of the birefringence pattern builder used for birefringence pattern fabrication is T1 [° C.] and the retardation disappearance temperature after exposure is T2 [° C.] (retardation) When the disappearing temperature is not in the temperature range of 250 ° C. or lower, T2 = 250), and the baking temperature is preferably T1 ° C. or higher and T2 ° C. or lower, more preferably (T1 + 10) ° C. or higher and (T2-5) ° C. or lower, Most preferable is (T1 + 20) ° C. or higher and (T2-10) ° C. or lower.
Baking reduces the retardation of the unexposed area in the birefringence pattern builder, while the exposed area where the retardation disappearance temperature has increased in the previous pattern exposure has little or no decrease in retardation. As a result, the retardation of the unexposed area becomes smaller than that of the exposed area, and a birefringence pattern (patterned optically anisotropic layer) is produced.
In order to exert an optical effect, the retardation of the exposed portion after baking is preferably 5 nm or more, more preferably 10 nm or more and 5000 nm or less, and most preferably 20 nm or more and 2000 nm or less. When the thickness is 5 nm or less, it is difficult to visually identify the produced birefringence pattern (see Table 1).

In order to exert an optical effect, the retardation after baking of the unexposed portion in the birefringence pattern builder is preferably 80% or less before baking, and 60% or less before baking. More preferably, it is more preferably 20% or less before baking, and most preferably less than 5 nm. In particular, when the retardation after baking is less than 5 nm, it gives an impression as if there was no birefringence at all visually. That is, black can be expressed under crossed Nicols, and colorless can be expressed under paranicols or on the polarizing plate + reflector. Thus, the birefringence pattern builder having a retardation of an unexposed portion after baking of less than 5 nm is useful when a color image is expressed by a birefringence pattern or when different patterns of a plurality of layers are laminated. It is.
For reference, when the optically anisotropic layer after baking (retardation before baking 100 nm) was visually observed under crossed Nicols, the remaining ratio and the unexposed area compared with the unexposed retardation before baking. Table 2 shows the ease of visual recognition of the difference between the exposed portions and the color of the unexposed portions in visual observation.

  Alternatively, a new birefringence pattern transfer material may be transferred onto the baked birefringence pattern material, and then a new pattern exposure and baking may be performed. In this case, the first and second unexposed areas, the first exposed area and the second unexposed area, the first unexposed area and the second exposed area ( The retardation of the first unexposed portion has already disappeared by baking), and the retardation value remaining after the second baking can be effectively changed in the first and second exposed regions. This method is useful when, for example, two regions having birefringences having different slow axis directions are not overlapped with each other.

[Functional layer laminated on birefringence pattern]
The birefringence pattern builder is an article having a birefringence pattern in which a birefringence pattern is prepared by performing exposure and baking as described above, and then a functional layer having various functions is further laminated. May be. Although it does not specifically limit as a functional layer, For example, the hard-coat layer which prevents the damage | wound of a surface, the reflection layer which makes easy the visual recognition of a birefringence pattern etc. are mention | raise | lifted. In order to facilitate identification, it is particularly preferable to have a reflective layer under the birefringence pattern.

[Article having birefringence pattern]
Articles obtained by exposing and baking a birefringence pattern builder as described above are usually almost colorless and transparent, but when sandwiched between two polarizing plates, or sandwiched between a reflective layer and a polarizing plate. In such a case, a characteristic brightness or darkness or color is shown and can be easily recognized visually. Taking advantage of this property, an article having a birefringence pattern obtained by the above manufacturing method can be used as, for example, a forgery prevention means. That is, an article having a birefringence pattern produced by the production method of the present invention, particularly an article having a birefringence pattern including a reflective layer is usually almost invisible by visual observation, but easily multicolored through a polarizing plate. Can be identified. When the birefringence pattern is copied without passing through the polarizing plate, nothing is reflected. Conversely, when the birefringence pattern is copied through the polarizing plate, it remains as a permanent pattern, that is, a visible pattern without the polarizing plate. Therefore, it is difficult to duplicate a birefringence pattern. Since a method for producing such a birefringence pattern is not widespread and the material is also special, it is considered suitable for use as a forgery prevention means.

[Optical element]
Further, an article having a birefringence pattern obtained by the above manufacturing method can be used for an optical element. For example, when an article having a birefringence pattern obtained by the above manufacturing method is used as a structural optical element, it is possible to produce a special optical element that is effective only for specific polarized light. As an example, the diffraction grating produced by the refractive index pattern of the present invention functions as a polarization separation element that strongly diffracts specific polarized light, and can be applied to the projector and optical communication fields.

[Liquid crystal display substrate]
Further, the article having a birefringence pattern may be a substrate for a liquid crystal display device.
It is preferable that the region (exposed portion) having retardation Re1 in the obtained optically anisotropic layer exhibits biaxiality, because a liquid crystal cell, particularly a VA mode liquid crystal cell can be accurately optically compensated. When a rod-like liquid crystal compound having a reactive group is used as the liquid crystal compound, polarized light is applied to the cholesteric alignment or the twisted hybrid cholesteric alignment while the inclination angle gradually changes in the thickness direction in order to develop biaxiality. It is necessary to distort by. As a method for distorting the alignment by polarized light irradiation, a method using a dichroic liquid crystalline polymerization initiator (EP 1389199 A1) or a method using a rod-like liquid crystalline compound having a photo-alignment functional group such as a cinnamoyl group in the molecule (special feature). Open 2002-6138). Any of them can be used in the present invention.

It is preferable that the optically anisotropic layer is a positive a-plate because a VA mode or transflective liquid crystal cell can be optically compensated accurately. Moreover, it is preferable that the optically anisotropic layer is a positive c-plate because the IPS mode can be optically compensated accurately.
In either case of the VA mode or the IPS mode, one of the polarizing plate protective films is preferably an optical compensation sheet. In the VA mode, the optically anisotropic layer as the polarizing plate protective film is preferably c-plate, and the IPS mode is preferably biaxial with the smallest refractive index in the thickness direction. The uniaxial optically anisotropic layer used in the transfer material of the present invention can be produced by aligning a uniaxial rod-like liquid crystalline compound so that the directors of the liquid crystal are aligned in one direction. Such uniaxial alignment includes a method of aligning a non-chiral liquid crystal layer on a rubbing alignment layer or photo-alignment layer, a method of aligning with a magnetic field or an electric field, a method of aligning by applying an external force such as stretching or shearing, etc. Can be realized.
In the present invention, the uniaxial or uniaxial orientation is formed on the substrate, or the one formed on the temporary support is transferred onto the substrate to form a uniform optical anisotropic layer on the entire surface, Patterns having different retardations of Re1 and Re2 (Re1> Re2) can be obtained by pattern exposure directly or through a photomask and further heating. The exposed part is preferably Re1. Re2 is preferably 80% or less of Re1, and more preferably 50% or less of Re1.

  Further, when forming a step, development with a liquid is performed before the heating step. There are no particular restrictions on the developer used in the development process after exposure, but alkali development is preferred from the viewpoint of environment and explosion-proof, and a known developer such as that described in JP-A-5-72724 is used. can do. The developer preferably has a development behavior in which the resin layer has a dissolution type. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. Further, a known surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

  As a development method, a known method such as paddle development, shower development, shower & spin development, dip development or the like can be used. By spraying a developer onto the exposed resin layer with a shower, the uncured portion can be removed. In addition, it is preferable to spray an alkaline solution having a low solubility of the resin layer by a shower or the like before development to remove the thermoplastic resin layer, the intermediate layer, and the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. As the cleaning liquid, known ones can be used, including (phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD1 (manufactured by Fuji Photo Film Co., Ltd.)”, or Sodium carbonate / phenoxyoxyethylene surfactant-containing, trade name “T-SD2 (Fuji Photo Film Co., Ltd.)”) is preferred. The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

(Preparation of coating liquid CU-1 for mechanical property control layer (thermoplastic resin layer))
The following composition was prepared, filtered through a polypropylene filter having a pore diameter of 30 μm, and used as a coating liquid CU-1 for a thermoplastic resin layer.
──────────────────────────────────――
Coating composition for mechanical property control layer (mass%)
──────────────────────────────────――
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55/30/10/5, weight average molecular weight = 100,000, Tg≈70 ° C.)
5.89
Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 65/35, weight average molecular weight = 10,000, Tg≈100 ° C.)
13.74
BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.20
Megafuck F-780-F (manufactured by Dainippon Ink & Chemicals, Inc.) 0.55
Methanol 11.22
Propylene glycol monomethyl ether acetate 6.43
Methyl ethyl ketone 52.97
──────────────────────────────────――

(Preparation of coating liquid AL-1 for alignment layer)
The following composition was prepared, filtered through a polypropylene filter having a pore size of 30 μm, and used as the intermediate layer / alignment layer coating solution AL-1.
──────────────────────────────────――
Coating solution composition for intermediate layer / alignment layer (% by mass)
──────────────────────────────────――
Polyvinyl alcohol (PVA205, manufactured by Kuraray Co., Ltd.) 3.21
Polyvinylpyrrolidone (Luvitec K30, manufactured by BASF) 1.48
Distilled water 52.1
Methanol 43.21
──────────────────────────────────――

(Preparation of coating liquid LC-1 for optically anisotropic layer)
After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-1 for an optically anisotropic layer.
LC-1-1 was synthesized based on the method described in JP-A No. 2004-123882. LC-1-1 is a liquid crystal compound having two reactive groups. One of the two reactive groups is an acrylic group which is a radical reactive group, and the other is an oxetane group which is a cationic reactive group. is there.
LC-1-2 is Tetrahedron Lett. It was synthesized according to the method described in Journal, Vol. 43, page 6793 (2002).

───────────────────────────────────────
Coating liquid composition for optically anisotropic layer (% by mass)
───────────────────────────────────────
Rod-shaped liquid crystal (LC-1-1) 19.57
Horizontal alignment agent (LC-1-2) 0.01
Cationic photopolymerization initiator (Cyracure UVI 6974, manufactured by Dow Chemical) 0.40
Polymerization control agent (IRGANOX1076, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.02
Methyl ethyl ketone 80.0
───────────────────────────────────────

(Preparation of coating liquid LC-2 for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-2 for an optically anisotropic layer.
LC-1-1 and LC-2-1 are liquid crystal compounds having two reactive groups, one of the two reactive groups is an acrylic group which is a radical reactive group, and the other is a cationic reactive group. It is an oxetane group.

───────────────────────────────────────
Coating liquid composition for optically anisotropic layer (% by mass)
───────────────────────────────────────
Rod-shaped liquid crystal (LC-1-1) 9.79
Rod-shaped liquid crystal (LC-2-1) 9.78
Horizontal alignment agent (LC-1-2) 0.01
Cationic photopolymerization initiator (Cyracure UVI 6974, manufactured by Dow Chemical) 0.40
Polymerization control agent (IRGANOX1076, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.02
Methyl ethyl ketone 80.0
───────────────────────────────────────

(Preparation of coating liquid LC-3 for optically anisotropic layer)
After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-3 for an optically anisotropic layer.
LC-3-1 was synthesized based on the method described in WO93 / 22397. LC-3-1 is a liquid crystal compound having two reactive groups, and both of the two reactive groups are acrylic groups which are radical reactive groups.
────────────────────────────────────────
Coating liquid composition for optically anisotropic layer (% by mass)
────────────────────────────────────────
Rod-like liquid crystal (LC-3-1) 31.93
Horizontal alignment agent (LC-1-2) 0.07
Radical photopolymerization initiator (IRGACURE907, manufactured by Ciba Specialty Chemicals) 1.00
Photopolymerization accelerator (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.)
0.33
Methyl ethyl ketone 66.67
────────────────────────────────────────

(Preparation of coating liquid LC-4 for optically anisotropic layer)
After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-4 for an optically anisotropic layer.
LC-4-1 and LC-4-2 were synthesized based on the method described in DJ Broer et al., Makromol. Chem. 190, 3201-3215 (1989).
LC-4-3 was synthesized based on the method described in British Patent No. 2280445.
LC-3-1 is a liquid crystal compound having two reactive groups, and both of the two reactive groups are acrylic groups which are radical reactive groups.
LC-4-1, LC-4-2, LC-4-3, and LC-4-4 are liquid crystal compounds having one reactive group, and the reactive group is an acrylic that is a radical reactive group. It is a group.

────────────────────────────────────────
Coating liquid composition for optically anisotropic layer (% by mass)
────────────────────────────────────────
Bar-shaped liquid crystal (LC-3-1) 2.00
Bar-shaped liquid crystal (LC-4-1) 10.77
Rod-like liquid crystal (LC-4-2) 8.33
Rod-like liquid crystal (LC-4-3) 4.17
Rod-shaped liquid crystal (LC-4-4) 3.33
Rod-shaped compound (LC-4-5) 3.33
Horizontal alignment agent (LC-1-2) 0.07
Radical photopolymerization initiator (IRGACURE907, manufactured by Ciba Specialty Chemicals) 1.00
Photopolymerization accelerator (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.)
0.33
Methyl ethyl ketone 66.67
────────────────────────────────────────

(Preparation of coating solution AD-1 for transfer adhesive layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating solution AD-1 for transfer adhesive layer.
────────────────────────────────────
Coating solution composition for transfer adhesive layer (% by mass)
────────────────────────────────────
Benzyl methacrylate / methacrylic acid / methyl methacrylate = 35.9 / 22.4 / 41.7 molar ratio random copolymer (weight average molecular weight 38,000) 8.05
KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 4.83
Radical photopolymerization initiator (2-trichloromethyl-5- (p-styrylstyryl)
1,3,4-oxadiazole) 0.12
Hydroquinone monomethyl ether 0.002
Megafuck F-176PF (Dainippon Ink Chemical Co., Ltd.) 0.05
Propylene glycol monomethyl ether acetate 34.80
Methyl ethyl ketone 50.538
Methanol 1.61
────────────────────────────────────

(Example 1: Preparation of birefringence pattern builder and article having birefringence pattern)
(Preparation of optically anisotropic layer check sample TRC-1 and birefringence pattern transfer material TR-1)
On the temporary support of a 100 μm-thick easy-adhesive polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.), in order using a wire bar, the coating liquid CU-1 for the mechanical property control layer, for the alignment layer The coating liquid AL-1 was applied and dried. The dry film thicknesses were 14.6 μm and 1.6 μm, respectively. Next, the coating liquid LC-1 for optically anisotropic layer was applied using a wire bar, dried at a film surface temperature of 105 ° C. for 2 minutes to form a liquid crystal phase, and then an air-cooled metal halide lamp of 160 W / cm in air. (Igraphics Co., Ltd.) is used to irradiate ultraviolet rays to fix the alignment state to form an optically anisotropic layer having a thickness of 2.4 μm. Produced. The illuminance of ultraviolet rays used at this time was 50 mW / cm ² in the UV-B region (integration of wavelengths 280 nm to 320 nm), and the irradiation amount was 35 mJ / cm ² in the UV-B region. The optically anisotropic layer of TRC-1 was a solid polymer at 20 ° C. and exhibited MEK (methyl ethyl ketone) resistance.

  Finally, a transfer adhesive layer coating solution AD-1 is applied on the optically anisotropic layer check sample TRC-1 and dried to form a 1.0 μm transfer adhesive layer, and then a protective film (12 μm thick polypropylene). Film) was pressure-bonded to prepare a birefringence pattern transfer material TR-1.

(Preparation of optical anisotropic layer check sample TRC-1-2 and transfer material TR-1-2 for birefringence pattern preparation of comparative example)
An optically anisotropic layer check sample TRC-1-2 and a birefringence pattern-preparing transfer material TR-1 are the same as TRC-1 and TR-1, except that the optically anisotropic layer is not irradiated with ultraviolet rays at all. -2 was produced. The optically anisotropic layer of TRC-1-2 was a low molecular weight solid at 20 ° C. and did not exhibit MEK resistance.

(Preparation of optical anisotropic layer check sample TRC-2 of comparative example and transfer material TR-2 for birefringence pattern preparation)
On the temporary support of a 100 μm-thick easy-adhesive polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.), in order using a wire bar, the coating liquid CU-1 for the mechanical property control layer, for the alignment layer The coating liquid AL-1 was applied and dried. The dry film thicknesses were 14.6 μm and 1.6 μm, respectively. Next, the coating liquid LC-2 for optically anisotropic layer was applied using a wire bar, dried at a film surface temperature of 95 ° C. for 2 minutes to form a liquid crystal phase, and then an air-cooled metal halide lamp of 160 W / cm in the air. (Igraphics Co., Ltd.) is used to irradiate ultraviolet rays to fix the alignment state to form an optically anisotropic layer having a thickness of 2.4 μm. Produced. The illuminance of ultraviolet rays used at this time was 240 mW / cm ² in the UV-A region (integration of wavelengths from 320 nm to 400 nm), and the irradiation amount was 200 mJ / cm ² in the UV-A region. The optically anisotropic layer of TRC-2 is a polymer that is solid at 20 ° C., but did not exhibit MEK resistance.

  Finally, a transfer adhesive layer coating solution AD-1 is applied on the optically anisotropic layer check sample TRC-2 and dried to form a 1.0 μm transfer adhesive layer, followed by a protective film (thickness 12 μm polypropylene film). ) Was pressure-bonded to prepare a birefringence pattern transfer material TR-2.

(Preparation of optical anisotropic layer check sample TRC-3 of comparative example and transfer material TR-3 for birefringence pattern preparation)
On the temporary support of a 100 μm-thick easy-adhesive polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.), in order using a wire bar, the coating liquid CU-1 for the mechanical property control layer, for the alignment layer The coating liquid AL-1 was applied and dried. The dry film thicknesses were 14.6 μm and 1.6 μm, respectively. Next, the coating liquid LC-3 for optically anisotropic layer was applied using a wire bar, dried at a film surface temperature of 105 ° C. for 2 minutes to form a liquid crystal phase, and then an air-cooled metal halide lamp of 160 W / cm under nitrogen (Igraphics Co., Ltd.) is used to irradiate ultraviolet rays to fix the alignment state to form an optically anisotropic layer having a thickness of 1.8 μm. Produced. The illuminance of ultraviolet rays used at this time was 100 mW / cm ² in the UV-A region (integration of wavelengths from 320 nm to 400 nm), and the irradiation amount was 80 mJ / cm ² in the UV-A region. The optically anisotropic layer of TRC-3 was a solid polymer at 20 ° C. and exhibited MEK resistance.

  Finally, coating liquid AD-1 for transfer adhesive layer is applied on optically anisotropic layer check sample TRC-3 and dried to form a 1.0 μm transfer adhesive layer, and then a protective film (thickness 12 μm polypropylene film). ) Was pressure-bonded to prepare a birefringence pattern transfer material TR-3.

(Preparation of optical anisotropic layer check sample TRC-4 of comparative example and transfer material TR-4 for birefringence pattern preparation)
On the temporary support of a 100 μm-thick easy-adhesive polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.), in order using a wire bar, the coating liquid CU-1 for the mechanical property control layer, for the alignment layer The coating liquid AL-1 was applied and dried. The dry film thicknesses were 14.6 μm and 1.6 μm, respectively. Next, the coating liquid LC-4 for optically anisotropic layer was applied using a wire bar, dried at a film surface temperature of 90 ° C. for 2 minutes to form a liquid crystal phase, and then a 160 W / cm air-cooled metal halide lamp under nitrogen. (Igraphics Co., Ltd.) is used to irradiate ultraviolet rays to fix the alignment state to form an optically anisotropic layer having a thickness of 1.8 μm. Produced. The illuminance of ultraviolet rays used at this time was 100 mW / cm ² in the UV-A region (integration of wavelengths from 320 nm to 400 nm), and the irradiation amount was 80 mJ / cm ² in the UV-A region. The optically anisotropic layer of TRC-4 was a solid polymer at 20 ° C. and exhibited MEK resistance.

  Finally, a coating solution AD-1 for transfer adhesive layer is applied on the optically anisotropic layer check sample TRC-4 and dried to form a 1.0 μm transfer adhesive layer, and then a protective film (thickness 12 μm polypropylene film). ) Was pressure-bonded to prepare a birefringence pattern transfer material TR-4.

(Effect of characteristics of optically anisotropic layer on transfer material for birefringence pattern production)
Table 3 shows the state and MEK resistance of each of the optically anisotropic layer check samples of TRC-1 to 4, and whether the birefringence pattern production transfer materials TR-1 to 4 produced therefrom can withstand use. It was.

As can be seen from Table 3, the optical anisotropy layer of TRC-1-2 consisting of a low molecule and not having solvent resistance and the optical anisotropy of TRC-2 which is a polymer but does not have solvent resistance Since the layer loses the birefringence due to the application of the transfer adhesive layer, it cannot be used as the optically anisotropic layer of the transfer material for producing the birefringence pattern. On the other hand, TR-1, TR-3, and TR-4 optically anisotropic layers having solvent resistance can be used as optically anisotropic layers of birefringence pattern transfer materials.
Below, it compares about the birefringence pattern preparation material produced using TR-1, TR-3, and TR-4.

(Preparation of birefringence pattern builder BPM-1)
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM-603, Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

  After peeling off the protective film of the transfer material TR-1 for producing the birefringence pattern, a laminator (manufactured by Hitachi Industries (Lamic II type)) was used, and the substrate heated at 100 ° C. for 2 minutes was subjected to the rubber roller temperature. Lamination was performed at 130 ° C., linear pressure of 100 N / cm, and conveyance speed of 1.4 m / min. After lamination, the temporary support was peeled off to prepare a birefringence pattern builder BPM-1.

(Preparation of birefringence pattern builder BPM-3 of comparative example)
A birefringence pattern builder BPM-3 of a comparative example was prepared in the same manner as BPM-1 except that TR-3 was used instead of TR-1 as a transfer material for birefringence pattern builder.

(Preparation of birefringence pattern builder BPM-4 of comparative example)
A birefringence pattern builder BPM-4 as a comparative example was prepared in the same manner as BPM-1 except that TR-3 was used instead of TR-1 as a transfer material for birefringence pattern builder.

(Phase difference measurement)
For each sample of BPM-1, BPM-3, and BPM-4, the sample was tilted by ± 40 degrees with the front retardation at the wavelength of 545 nm and the fast axis as the rotation axis by the parallel Nicol method using a fiber spectrometer. The retardation at a wavelength of 545 nm was measured. Table 4 shows the phase difference measurement results.

(Measurement of retardation disappearance temperature)
About each sample of BPM-1, BPM-3, and BPM-4, pattern exposure was performed at an exposure amount of 50 mJ / cm ² using Mikasa M-3L mask aligner and photomask I (FIG. 8). Each of the exposed part and the unexposed part is observed from a Nikon Corporation Eclipse E600 Pol polarizing microscope while heating from a room temperature to 250 ° C. at a heating rate of 20 ° C. per minute on a Mettler hot stage, and the retardation disappearance temperature is measured. It was measured. The results are shown in Table 5.

  As a result of measuring the retardation disappearance temperature, only BPM-1 had different results in the exposed area and the unexposed area. This result is considered to be related to the presence or absence of an unreacted reactive group in each optically anisotropic layer, and thus to the structure of the liquid crystal compound used for the production of the optically anisotropic layer. That is, the optically anisotropic layer of BPM-1 has a cation-based light on the liquid crystal compound LC-1-1 having both an acrylic group which is a radical reactive group and the other oxetane group which is a cationic reactive group. It was prepared by adding a polymerization initiator and exposing it to cationic polymerization, and it is considered that an unreacted acrylic group remains, whereas the optically anisotropic layers of BPM-3 and BPM-4 are radical. It is considered that the liquid crystal compound having only the acrylic group, which is a reactive group, is prepared by adding a radical photopolymerization initiator and exposing it to radical polymerization, and it is considered that the unreacted reactive group is poor. Only -1 is considered to be the cause of different retardation disappearance temperatures in the exposed and unexposed areas. In any sample, the retardation that disappeared due to the temperature rise remained disappeared even when the temperature was returned to room temperature.

(Production of retardation pattern)
About each sample of BPM-1, BPM-3, and BPM-4, pattern exposure was performed with the exposure amount of 50 mJ / cm < ² > using the M-3L mask aligner and photomask I by Mikasa. Next, baking was performed in a clean oven at 230 ° C. for 1 hour to prepare corresponding retardation patterns BP-1, BP-3, and BP-4. Table 6 shows the results of measuring the unexposed area and the exposed area retardation of each sample.

The unexposed part has a retardation disappearance temperature, and the exposed part has a clear difference in retardation between the unexposed part and the exposed part of BP-1 having a retardation disappearance temperature of more than 250 ° C. On the other hand, a sample of BP-3 which originally does not show retardation disappearance temperature and BP-4 whose retardation disappearance temperature does not change before and after exposure does not cause a difference in retardation between the unexposed portion and the exposed portion.
The pattern observed when these samples are placed under crossed Nicols is shown in FIG. In the figure, a black solid portion is a portion that appears black under crossed Nicols, and a hatched portion is a portion that appears yellowish white under crossed Nicols. BP-1 having a retardation disappearance temperature before exposure and no longer exhibiting a retardation disappearance temperature after exposure produces a retardation pattern by sequentially performing pattern exposure and baking, and is yellowish white by visual observation under crossed Nicols. A clear black pattern was shown. BP-1 is observed in black under crossed Nicols because the retardation of the unexposed area is kept low, and thus a clear pattern display is possible.
On the other hand, in BP-3, retardation remains in both the unexposed area and the exposed area, and in BP-4, both the unexposed area and the exposed area have greatly reduced retardation. In either case, it is difficult to form a retardation pattern. It was.

(Example 2: Birefringence pattern builder made by laminating a plurality of optically anisotropic layers)
(Preparation of birefringence pattern transfer material TR-5)
A birefringence pattern transfer material TR-5 was prepared in the same manner as TR-1, except that the thickness of the optically anisotropic layer was 3.6 μm.
(Preparation of birefringence pattern builder BPM-5)
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM-603, Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

After peeling off the protective film of the birefringence pattern production transfer material TR-5, a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) and heated at 100 ° C. for 2 minutes on a substrate heated to a rubber roller temperature Lamination was performed at 130 ° C., linear pressure of 100 N / cm, and conveyance speed of 1.4 m / min.
After lamination, the birefringence pattern-preparing transfer material TR-5 was again laminated on the substrate after the temporary support was peeled off by the same method. At this time, attention was paid so that the slow axis directions of both the optically anisotropic layer laminated earlier and the optically anisotropic layer laminated later substantially coincided.
After the second lamination, the transfer material TR-1 for producing a birefringence pattern was further laminated on the substrate after the temporary support was peeled off by the same method. Also in this case, attention was paid so that the slow axis directions of the two optically anisotropic layers laminated previously and the optically anisotropic layer laminated this time were almost the same. After lamination, the temporary support was peeled off to prepare a birefringence pattern builder BPM-5 in which a plurality of optically anisotropic layers of Example 2 were laminated.

(Production of retardation pattern)
BPM-5 was subjected to pattern exposure at an exposure amount of 50 mJ / cm ² using Mikasa M-3L mask aligner and Photomask I. Next, baking was performed in a clean oven at 230 ° C. for 1 hour to prepare a retardation pattern BP-5. Table 7 shows the results of measuring the unexposed and exposed area retardation of the sample.

In the sample, the retardation of the unexposed part is extremely low, but a large retardation of about 800 nanometers is obtained in the exposed part.
The pattern observed when this sample is placed under crossed Nicols is shown in FIG. In the figure, the portion indicated by solid black is a portion that appears black under crossed Nicols, and the lattice portion is a portion that appears yellowish green under crossed Nicols. Thus, by laminating a plurality of optically anisotropic layers, a pattern with a large retardation value can be easily obtained.

(Example 3: Production of multicolor pattern by repeating transfer, exposure and baking plural times)
(Preparation of birefringence pattern transfer material TR-6)
A transfer material TR-6 for preparing a birefringence pattern was prepared in the same manner as TR-1, except that the thickness of the optically anisotropic layer was 1.2 μm.
(Preparation of multicolor birefringence pattern BP-6 of the present invention)
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM-603, Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

After peeling off the protective film of the birefringence pattern transfer material TR-1, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) is heated to a rubber roller temperature of 130. Lamination was performed at a temperature of 100 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.4 m / min.
After lamination, the substrate after peeling the temporary support was subjected to pattern exposure at an exposure amount of 50 mJ / cm ² using Mikasa M-3L mask aligner and Photomask II (FIG. 11). Next, baking was performed for 1 hour in a 230 ° C. clean oven.

A birefringence pattern-preparing transfer material TR-6 was laminated to the substrate after baking by the same method as described above. At this time, attention was paid so that the direction of the slow axis of the optically anisotropic layer of TR-1 previously laminated coincided with the direction of the slow axis of the optically anisotropic layer of TR-6 laminated this time.
After lamination, the substrate after peeling the temporary support was subjected to pattern exposure at an exposure amount of 50 mJ / cm ² using Mikasa M-3L mask aligner and Photomask III (FIG. 12). Furthermore, baking was performed in a clean oven at 230 ° C. for 1 hour to produce a multicolor birefringence pattern BP-6 of the present invention.
Table 8 shows the results of measuring the retardation of the unexposed portion, mask II exposed portion, and mask III exposed portion of the sample.

As the retardation of the sample, different values are obtained in the unexposed area, the mask II exposed area, and the mask III exposed area.
The pattern observed when this sample is placed under crossed Nicols is shown in FIG. In the figure, a black solid portion is a portion that appears black under crossed Nicols, a horizontal line portion is a portion that appears white under crossed Nicols, and a hatched portion is a portion that appears light yellow under crossed Nicols. Thus, by repeating the patterning of the plurality of optically anisotropic layers by repeating the cycle of transfer, pattern exposure, and baking, a multi-valued retardation pattern can be easily obtained.

(Example 4: Production of a birefringence pattern having a reflective layer)
(Preparation of birefringence pattern transfer material TR-7)
On a 75 μm-thick polyethylene terephthalate film temporary support, the coating liquid CU-1 for mechanical property control layer and the coating liquid AL-1 for alignment layer were sequentially applied and dried using a wire bar. The dry film thicknesses were 14.6 μm and 1.6 μm, respectively. Next, the coating liquid LC-1 for optically anisotropic layer was applied using a wire bar, dried at a film surface temperature of 105 ° C. for 2 minutes to form a liquid crystal phase, and then an air-cooled metal halide lamp of 160 W / cm in air. The optically anisotropic layer having a thickness of 1.7 μm was formed by fixing the alignment state by irradiating ultraviolet rays (made by Eye Graphics Co., Ltd.). The illuminance of ultraviolet rays used at this time was 50 mW / cm ² in the UV-B region (integration of wavelengths 280 nm to 320 nm), and the irradiation amount was 35 mJ / cm ² in the UV-B region. Finally, a photosensitive transfer adhesive layer coating solution AD-1 is applied and dried to form a 1.0 μm photosensitive transfer adhesive layer, and then a protective film (polypropylene film having a thickness of 12 μm) is pressure-bonded to form a birefringence pattern. A production transfer material TR-7 was produced.

(Preparation of birefringence pattern BP-7 having a reflective layer)
The aluminum vapor-deposited glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds with a shower. After pure water shower washing, a silane coupling solution (N-β (aminoethyl) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM-603, Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

After peeling off the protective film of the transfer material TR-7 for birefringence pattern preparation, a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) was used, and the substrate heated at 100 ° C. for 2 minutes was subjected to a rubber roller temperature of 130. Lamination was performed at a temperature of 100 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.4 m / min.
After lamination, the substrate after peeling the temporary support was subjected to pattern exposure with an exposure amount of 50 mJ / cm ² using Mikasa M-3L mask aligner and Photomask I.

Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoamer-containing, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) Shower development was performed at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa, and the mechanical property control layer and the alignment layer were removed. Thereafter, baking was performed in a clean oven at 230 ° C. for 1 hour, and the birefringence pattern BP of the present invention having a reflective layer -7 was produced.
The pattern observed when a polarizing plate is overlaid on this sample is shown in FIG. In the figure, the part shown in gray is the part that looks silver, and the wavy part is the part that looks blue-purple. As described above, the birefringence pattern can also be produced for reflection observation. In this case, the pattern can be easily identified only by holding the polarizing plate.

(Example 5: Production of birefringence pattern having a plurality of optically anisotropic layers having different slow axis directions)
(Preparation of birefringence pattern transfer material TR-8)
A transfer material TR-8 for producing a birefringence pattern was produced in the same manner as TR-7 except that the thickness of the optically anisotropic layer was changed to 3.4 μm.
(Preparation of birefringence pattern BP-8 having a plurality of optically anisotropic layers with different slow axis directions)
The aluminum vapor-deposited glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds with a shower. After pure water shower washing, a silane coupling solution (N-β (aminoethyl) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM-603, Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

After peeling off the protective film of the transfer material TR-7 for birefringence pattern preparation, a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) was used, and the substrate heated at 100 ° C. for 2 minutes was subjected to a rubber roller temperature of 130. Lamination was performed at a temperature of 100 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.4 m / min.
After laminating, the substrate after peeling the temporary support was treated with a triethanolamine developer (containing 2.5% triethanolamine, containing a nonionic surfactant, containing a polypropylene antifoaming agent, trade name: T-PD1, Shower development was performed at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa, and the mechanical property control layer and the alignment layer were removed.

Next, the birefringence pattern preparation transfer material TR-8 was laminated in the same manner. At this time, the slow axis direction of the optically anisotropic layer laminated later is shifted by 60 ° in the clockwise direction with respect to the slow axis direction of the optically anisotropic layer previously laminated. Laminated.
After the second lamination, the substrate after peeling the temporary support was subjected to pattern exposure using an M-3L mask aligner and a photomask I manufactured by Mikasa Co., Ltd. at an exposure amount of 50 mJ / cm ² .

Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoamer-containing, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) The birefringence pattern having the reflective layer of Example 5 was subjected to shower development at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the mechanical property control layer and the alignment layer and then baked in a clean oven at 230 ° C. for 1 hour. Was made.

  The pattern observed when a polarizing plate is overlaid on this sample is shown in FIG. At this time, the layers were stacked so that the direction of the transmission axis of the polarizing plate was shifted by 75 ° in the clockwise direction with respect to the direction of the slow axis of the optically anisotropic layer previously laminated. In the drawing, a gray portion is a portion that looks silver, and a black solid portion is a portion that looks black. When expressing an image with a birefringence pattern sandwiched between a reflective layer and a polarizing plate, a pattern having a broadband λ / 4 retardation is required to express black, and in a general uniaxial birefringence pattern, Although this is not possible, a birefringence pattern builder can easily produce a pattern having a broadband λ / 4 retardation by laminating a plurality of optically anisotropic layers, and a black pattern can be obtained.

(Example 6: Production of article using birefringence pattern as anti-counterfeiting means)
(Preparation of birefringence pattern BP-9 having a reflective layer)
A substrate in which an aluminum foil was temporarily fixed to glass with a heat-resistant tape was produced, and this substrate was heated at 100 ° C. for 2 minutes with a substrate preheating device.
After peeling off the protective film of the birefringence pattern transfer material TR-1, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) is heated to a rubber roller temperature of 130. Lamination was performed at a temperature of 100 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.4 m / min.
After lamination, the substrate after peeling the temporary support was subjected to pattern exposure at an exposure amount of 50 mJ / cm ² using Mikasa M-3L mask aligner and photomask IV (FIG. 16).

The birefringence pattern preparation transfer material TR-6 was again laminated on the exposed substrate by the same method. At this time, attention was paid so that the slow axis directions of both the optically anisotropic layer laminated earlier and the optically anisotropic layer laminated later substantially coincided.
After lamination, the substrate after peeling the temporary support was subjected to pattern exposure at an exposure amount of 50 mJ / cm ² using Mikasa M-3L mask aligner and photomask V (FIG. 17). Further, after baking for 1 hour in a clean oven at 230 ° C., the aluminum foil on which the birefringence pattern was laminated was removed from the glass plate to produce a multicolor birefringence pattern BP-9 on the reflective layer of the present invention. The enlarged view of the pattern observed through a polarizing plate on BP-9 is shown in FIG. In the figure, while the ground aluminum foil is silver, a two-color pattern is observed in which the lattice portion is dark blue and the shaded portion is yellow or orange.
FIG. 19 shows an example in which the produced birefringence pattern is cut into an appropriate size and attached to a gift certificate with an adhesive. The part of the authentication part in the figure is a reflection part provided with a birefringence pattern. Although the birefringence pattern of the authentication part is almost invisible by normal visual observation, it can be visually observed as a two-color pattern by holding the polarizing plate, and authenticity can be determined by the pattern.

(Example 7: Production of birefringence pattern using stretched polymer)
(Preparation of coating liquid OL-1 for optically anisotropic layer)
After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid OL-1 for an optically anisotropic layer.
OL-1-1 is a rod-shaped compound having two reactive groups, one of the two reactive groups is an acrylic group which is a radical reactive group, and the other is an oxetane group which is a cationic reactive group. is there.
OL-1-2 is a surfactant added for the purpose of improving coatability. Tetrahedron Lett. It was synthesized according to the method described in Journal, Vol. 43, page 6793 (2002).

───────────────────────────────────────
Coating liquid composition for optically anisotropic layer (% by mass)
───────────────────────────────────────
Rod-shaped compound (OL-1-1) 29.17
Horizontal alignment agent (CL-2-1) 0.10
Crystalline control agent (Paliocolor LC756, BASF Japan)
3.33
Cationic photopolymerization initiator (CPI100-P, manufactured by San Apro Co., Ltd.) 0.67
Polymerization control agent (IRGANOX1076, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.07
Methyl ethyl ketone 66.66
───────────────────────────────────────

(Preparation of birefringence pattern transfer material TR-10)
On a 75 μm-thick polyethylene terephthalate film temporary support, the coating liquid CU-1 for mechanical property control layer and the coating liquid AL-1 for alignment layer were sequentially applied and dried using a wire bar. The dry film thicknesses were 14.6 μm and 1.6 μm, respectively. Next, the coating liquid OL-1 for optically anisotropic layer was applied using a wire bar, dried at a film surface temperature of 110 ° C. for 2 minutes, and then air-cooled metal halide lamp (eye graphics Co., Ltd.) of 160 mW / cm under air. )) Was used to irradiate ultraviolet rays to fix the orientation state, and an optically anisotropic layer having a thickness of 3.5 μm was formed. The illuminance of ultraviolet rays used at this time was 100 mW / cm ² in the UV-A region (integration of wavelengths from 320 nm to 400 nm), and the irradiation amount was 80 mJ / cm ² in the UV-A region.
Next, a transfer adhesive layer coating solution AD-1 was applied on the optically anisotropic layer and dried to form a 1.2 μm transfer adhesive layer. Finally, the prepared sample was stretched 50% at 90 ° C. at a rate of 10 mm / min using a universal testing machine Tensilon to prepare a birefringence pattern preparing transfer material TR-10. The optical functional layer of TR-10 was a solid polymer at 20 ° C. and exhibited MEK resistance.

(Preparation of birefringence pattern builder BPM-10)
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM-603, Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.
The transfer material TR-10 for producing a birefringence pattern was heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)). Lamination was performed at 100 N / cm and a conveyance speed of 1.4 m / min. After lamination, the temporary support was peeled off to prepare a birefringence pattern builder BPM-10.

(Preparation of birefringence pattern)
BPM-10 was subjected to pattern exposure at an exposure amount of 50 mJ / cm ² using Mikasa M-3L mask aligner and Photomask I.
Thereafter, 30 in a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoaming agent, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) Shower development was performed at 50 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa, and the mechanical property control layer and the alignment layer were removed. Thereafter, baking was performed in a clean oven at 230 ° C. for 1 hour to prepare the birefringence pattern BP-10 of the present invention. . Table 9 shows the results of measuring the retardation of the unexposed and exposed areas of the sample.

  The produced sample showed a birefringence pattern having different retardations in the unexposed area and the exposed area. Thus, the birefringence pattern material of the present invention can also be produced using a stretching method. When the birefringence pattern material is produced by a stretching method, the optical anisotropic layer of the optical anisotropic layer can be adjusted depending on the degree of stretching.

(Examples 8 and 9: Production of transfer material having phase difference of λ / 2 and λ / 4)
(Production of transfer material of Example 8)
On the temporary support of a 100 μm-thick easy-adhesive polyethylene terephthalate film (Cosmo Shine A4100, manufactured by Toyobo Co., Ltd.), in order using a wire bar, the coating solution CU-1 for the thermoplastic resin layer, for the alignment layer The coating liquid AL-1 was applied and dried. The dry film thicknesses were 14.6 μm and 1.6 μm, respectively. Next, LC-1 was applied using a wire bar, dried at a film surface temperature of 105 ° C. for 2 minutes to form a liquid crystal phase, and then an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm under air. ) To irradiate ultraviolet rays having an illuminance of 240 mW / cm ² and an irradiation amount of 600 mJ / cm ² to fix the alignment state, and form an optically anisotropic layer having a thickness of 3.5 μm. The transfer material of Example 8 was produced by applying and drying the coating liquid AD-1 for adhesive transfer adhesive layer to form a photosensitive resin layer having a thickness of 1.0 μm.

(Preparation of transfer material of Example 9)
A transfer material of Example 9 was produced in the same manner as Example 8 except that the thickness of the optically anisotropic layer was 1.8 μm.
(Phase difference measurement)
By the parallel Nicol method using a fiber spectrometer, the front retardation at a wavelength of 545 nm and the retardation at a wavelength of 545 nm when the sample is tilted by ± 40 degrees with the slow axis as the rotation axis were measured. Table 10 shows the phase difference measurement results.

(Examples 10 and 11: Production of a substrate for a liquid crystal display device having a retardation pattern using transfer to a substrate)
(Production of substrates for liquid crystal display devices)
A color filter substrate having a black matrix and three color filters of RGB was formed on a glass substrate by a general method described in Kosuke Kobayashi, Color Liquid Crystal Display, page 240, Sangyo Tosho (1994). In addition, the transfer material of Example 8 was heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), a rubber roller temperature of 130 ° C., and a linear pressure of 100 N. / Cm, laminating at a conveyance speed of 2.2 m / min.
After peeling the temporary support, the exposure mask with the substrate and mask (quartz exposure mask with image pattern) standing upright with a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultra high pressure mercury lamp. The distance between the surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 25 mJ / cm ² .

  Next, it was baked in a muffle furnace at 230 ° C. for 1 hour to prepare a substrate for a liquid crystal display device of Example 10 having the retardation pattern of the embodiment of FIG. Further, a liquid crystal display device substrate of Example 11 was produced in the same manner as Example 10 except that the transfer material of Example 9 was used.

(Examples 12 and 13: Production of a substrate for a liquid crystal display device having a retardation and a step pattern using transfer to a substrate)
On the color filter substrate used in Example 10, the transfer material of Example 8 was laminated in the same manner as in Example 10, the temporary support was peeled off, and then the photosensitive resin layer coating solution AD-1 was applied by spin coating. A photosensitive resin layer having a thickness of 2.0 μm was formed. Next, with a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the photosensitivity The distance between the resin layers was set to 200 μm, and pattern exposure was performed with an exposure amount of 25 mJ / cm ² . Further, Na carbonate developer (0.06 mol / L sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T -CD1, manufactured by Fuji Photo Film Co., Ltd.), the photosensitive resin layer was developed by shower development with a cone-type nozzle pressure of 0.15 MPa to obtain a stepped layer.

  Subsequently, using a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD1” (manufactured by Fuji Photo Film Co., Ltd.)) at a cone type nozzle pressure of 0.02 MPa. After removing the residue with a rotary brush having a shower and nylon hair, the liquid crystal display of Example 12 in the form of FIG. 4D having a pattern of retardation by baking for 1 hour in a muffle furnace at 230 ° C. A device substrate was prepared, and a liquid crystal display device substrate of Example 13 was prepared in the same manner as Example 12 except that the transfer material of Example 9 was used. Table 11 shows the measurement of the pattern.

(Example 14: Production of transflective LCD using liquid crystal display substrate having retardation and step pattern)
A transflective ECB-LCD was manufactured by forming an alignment film made of a transparent electrode and polyimide on the liquid crystal display device substrate of Example 13, and using a TFT substrate with a reflective plate as the opposite liquid crystal display device substrate.
Same as Example 14 except that a liquid crystal display device substrate prepared in the same manner as the liquid crystal display device substrate of Example 13 by performing overall exposure instead of pattern exposure was used instead of the liquid crystal display device substrate of Example 13. Comparative Example 14-2 A liquid crystal display device substrate prepared in the same manner as the liquid crystal display device substrate of Example 13 except that it was not exposed at all instead of pattern exposure. The same thing as Example 14 was produced as Comparative Example 14-3 except having used instead. Further, a transflective ECB-LCD configured as shown in FIG. 7B was produced as Comparative Example 14-4. Table 12 shows the visual evaluation results of Example 14 and Comparative Examples 14-2 to 14-4.

(Example 15: Production of a substrate for a liquid crystal display device having a retardation pattern using direct application to a substrate)
The alkali-free glass substrate was washed with a rotating brush having nylon bristles while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds with a shower, and a pure water shower was performed. The glass substrate was heated at 100 ° C. for 2 minutes with a substrate preheating apparatus.
On the glass substrate, a color filter substrate having a black matrix and RGB color filters was formed by a general method described in Kobayashi Keisuke, Color Liquid Crystal Display, page 240, Sangyo Tosho (1994).

A commercially available coating liquid for alignment layer (RN1199A, manufactured by Nissan Chemical Industries, Ltd.) was applied onto the color filter substrate, dried and baked at 220 ° C. for 1 hour to prepare an alignment layer. The thickness of the substrate after firing was 60 nm.
Next, the alignment layer was subjected to a rubbing treatment, and an optically anisotropic layer coating liquid LC-1 was applied onto the alignment layer. This was dried at a film surface temperature of 105 ° C. for 2 minutes to form a liquid crystal phase, and then an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) having an illuminance of 240 mW / cm ² in air, The alignment state was fixed by irradiating with an irradiation amount of 600 mJ / cm ² to form a substrate for a liquid crystal display device having a thickness of 1.8 μm before pattern formation in the embodiment of FIG.

Subsequently, a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having a super high pressure mercury lamp, which is coated with a coating solution AD-1 for photosensitive transfer adhesive layer and dried to form a photosensitive resin layer of 2.0 μm. Then, the distance between the exposure mask surface and the photosensitive resin layer was set to 100 μm, and pattern exposure was performed at an exposure amount of 100 mJ / cm ² .
Further, Na carbonate developer (0.06 mol / L sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T -CD1, manufactured by Fuji Photo Film Co., Ltd.), the photosensitive resin layer was developed by shower development with a cone-type nozzle pressure of 0.15 MPa to obtain a stepped layer.

Subsequently, using a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD1” (manufactured by Fuji Photo Film Co., Ltd.)) at a cone type nozzle pressure of 0.02 MPa. The residue was removed with a shower and a rotating brush with nylon bristles.
Finally, baking was performed in a muffle furnace at 230 ° C. for 1 hour to prepare a liquid crystal display device substrate of Example 15 having a retardation pattern.
Further, a retardation measurement substrate was produced in the same manner as in Example 15 except that the color filter was not formed on the glass substrate in the production method of the liquid crystal display device substrate of Example 15.

(Phase difference measurement)
Using the retardation measurement substrate, a tilt at 545 nm when the sample is tilted ± 40 degrees around the front retardation Re and the slow axis at the wavelength λ by the parallel Nicol method using a fiber spectrometer. A retardation of 40 ° and a retardation of −40 ° obliquely were measured. Table 13 shows the retardation measurement results before baking at 230 ° C. for 1 hour, and Table 14 shows the retardation measurement results after baking.
Here, the oblique 40 ° retardation is measured by injecting light having a wavelength of 545 nm from a direction inclined + 40 ° with respect to the normal direction in the plane with the in-plane slow axis as the tilt axis (rotation axis). Represents the retardation.

(Example 16: Production of transflective LCD)
A transflective VA-LCD was produced by forming an alignment film made of a transparent electrode and polyimide on the liquid crystal display device substrate of Example 15, and using a TFT substrate with a reflective plate as the opposite liquid crystal display device substrate.

  Example 16 except that a liquid crystal display device substrate prepared in the same manner as the liquid crystal display device substrate of Example 15 was used instead of the liquid crystal display device substrate of Example 15 except that the entire surface was exposed instead of pattern exposure. Similarly, a liquid crystal display device substrate prepared in the same manner as the liquid crystal display device substrate of Example 15 except that the LCD of Comparative Example 16-2 was not exposed at all instead of pattern exposure. An LCD of Comparative Example 16-3 was produced in the same manner as in Example 16 except that it was used instead of the substrate. Further, a transflective VA-LCD having a structure shown in FIG. 7B was manufactured as Comparative Example 16-4. Table 15 shows the visual evaluation results of Example 16 and Comparative Examples 16-2 to 4-4.

It is a schematic sectional drawing which shows the example of a birefringence pattern preparation material. It is a schematic sectional drawing of the example of the birefringence pattern preparation material used as a transfer material It is a schematic sectional drawing of the example of the articles | goods which have a birefringence pattern obtained by the manufacturing method of this invention. It is a schematic sectional drawing of an example of the board | substrate for liquid crystal display devices obtained by the manufacturing method of this invention. It is a schematic sectional drawing of an example of the transfer material used for the manufacturing method of the board | substrate for liquid crystal display devices of this invention. It is the schematic of an example of the board | substrate for liquid crystal display devices which has a color filter layer obtained by the manufacturing method of this invention. It is a schematic sectional drawing of an example of the liquid crystal display device which has the board | substrate for liquid crystal display devices obtained by the manufacturing method of this invention. It is a figure which shows the shape of the photomask I used in the Example. The white part is the exposed part and the black part is the unexposed part. It is a schematic diagram of a pattern when the article which has the birefringence pattern produced in Example 1 is observed under crossed Nicols. It is a schematic diagram of a pattern when the article which has the birefringence pattern produced in Example 2 is observed under crossed Nicols. It is a figure which shows the shape of the photomask II used in the Example. The white part is the exposed part and the black part is the unexposed part. It is a figure which shows the shape of the photomask III used in the Example. The white part is the exposed part and the black part is the unexposed part. It is a schematic diagram of a pattern when the article which has the birefringence pattern produced in Example 3 is observed under crossed Nicols. It is a schematic diagram of a pattern when the article which has the birefringence pattern produced in Example 4 is observed under crossed Nicols. It is a schematic diagram of a pattern when the article which has the birefringence pattern produced in Example 5 is observed under crossed Nicols. It is a figure which shows the shape of the photomask IV used in the Example. The white part is the exposed part and the black part is the unexposed part. It is a figure which shows the shape of the photomask V used in the Example. The white part is the exposed part and the black part is the unexposed part. It is an enlarged view of the pattern observed when the article which has the birefringence pattern produced in Example 5 is observed through a polarizing plate. It is a figure which shows the example which cut | disconnected the goods which have the birefringence pattern produced in Example 5 to a suitable magnitude | size, and affixed on the gift certificate with the adhesive.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Support body or substrate 12 Optically anisotropic layer 12A Optically anisotropic layer exposed part 12B Optically anisotropic layer unexposed part 12F First optically anisotropic layer 12S Second optically anisotropic layer 13 Orientation layer ( On the support)
14 Transfer Adhesive Layer 14A First Transfer Adhesive Layer 14B Second Transfer Adhesive Layer 14C Third Transfer Adhesive Layer 15 Photosensitive Resin Layer 16 Back Adhesive Layer 17 Release Layer 18 Surface Protective Layer 21 Temporary Support 22 Orientation Layer (Temporary Support Up)
22F First orientation layer on temporary support 22S First orientation layer on temporary support 23 Mechanical property control layer 112 Patterned optical anisotropic layer 112-A Patterned optical anisotropic layer (exposed part)
112-B Patterned optically anisotropic layer (unexposed part)
112F-A Patterned first optically anisotropic layer (exposed part)
112F-B Patterned first optically anisotropic layer (unexposed part)
112S-A Patterned second optically anisotropic layer (exposed part)
112S-B Patterned second optically anisotropic layer (unexposed part)
112T-A Patterned third optically anisotropic layer (exposed part)
112T-B Patterned third optically anisotropic layer (unexposed part)
24 Temporary support for transfer material 31 for transfer to temporary support 21 Black matrix 32 Color filter layer 33 Transmission part 34 Reflection part 35 Reflection layer 41 Polarization layer 42 Cellulose acetate film (polarizing plate protective film)
43 Cellulose acetate film or optical compensation sheet 43A λ / 2 plate 43B λ / 4 plate 44 Adhesive layer 45 Drive element 46 Reflector plate 47 Liquid crystal 48 Liquid crystal display substrate 49 Polarizing plate

Claims (35)

A method for producing an article having a birefringence pattern including at least the following steps [1] to [3] in this order:
[1] An optically anisotropic layer containing a polymer,
The optically anisotropic layer has a retardation disappearing temperature at which the in-plane retardation is 30% or less of the retardation at 20 ° C. in a temperature range higher than 20 ° C., and the retardation disappearing temperature is increased by exposure. Preparing a birefringence pattern builder material;
[2] A step of performing pattern exposure on the birefringence pattern builder;
[3] A step of heating the laminate obtained after step 2 to 50 ° C. or higher and 400 ° C. or lower. The production method according to claim 1, wherein the rising retardation disappearance temperature of the birefringence pattern builder is not in a temperature range of 250 ° C. or lower. The production method according to claim 1 or 2, wherein the in-plane retardation of the birefringence pattern builder at 20 ° C is 10 nm or more. The manufacturing method according to claim 1, wherein the polymer has an unreacted reactive group. 2. The optically anisotropic layer is formed by applying and drying a solution containing a liquid crystal compound having at least one reactive group to form a liquid crystal phase, and then polymerizing and fixing by irradiation with heat or ionizing radiation. The manufacturing method of any one of -4. The production method according to claim 5, wherein the liquid crystalline compound has two or more types of reactive groups having different polymerization conditions. The production method according to claim 5, wherein the liquid crystal compound has at least a radical reactive group and a cationic reactive group. The production method according to claim 7, wherein the radical reactive group is an acryl group and / or a methacryl group, and the cationic group is a vinyl ether group, an oxetane group and / or an epoxy group. The manufacturing method according to claim 1, wherein the optically anisotropic layer is made of a stretched film. The method according to claim 1, wherein the birefringence pattern builder includes two or more optically anisotropic layers. The manufacturing method according to claim 10, wherein the two or more optically anisotropic layers include at least two optically anisotropic layers having different slow axis directions and / or in-plane retardation. The manufacturing method according to claim 1, wherein the optically anisotropic layer is a layer provided by transferring a transfer material including the optically anisotropic layer onto a material to be transferred. . The manufacturing method according to any one of claims 1 to 12, comprising the following steps 13 and 14 in this order after the step 2 and before the step 3:
[13] A step of transferring another birefringence pattern builder to the laminate obtained after step 2;
[14] A step of performing pattern exposure on the laminate obtained after the transfer. The manufacturing method of any one of Claims 1-12 including the following processes 24-26 in this order after the said process 3.
[24] A step of transferring another birefringence pattern builder to the laminate obtained after step 3;
[25] A step of performing pattern exposure on the laminate obtained after step 24;
[26] A step of heating the laminate obtained after step 25 to 50 ° C. or higher and 400 ° C. or lower. The birefringence pattern builder has a photosensitive resin layer on an optically anisotropic layer, and in step 2, the birefringence pattern builder is subjected to pattern exposure from the photosensitive resin layer side, and The manufacturing method according to any one of claims 1 to 12, further comprising the following step 9:
[9] A step of removing an unnecessary photosensitive resin layer on the laminate. The article | item used as a forgery prevention means obtained by the manufacturing method of any one of Claims 1-15. The optical element obtained by the manufacturing method of any one of Claims 1-15. The substrate for liquid crystal display devices obtained by the manufacturing method of any one of Claims 1-15. Comprising an optically anisotropic layer comprising a polymer;
The optically anisotropic layer has a retardation disappearance temperature at which the in-plane retardation is 30% or less of the retardation at 20 ° C in a temperature range higher than 20 ° C, and the retardation disappearance temperature is increased by exposure. Birefringence pattern builder. The birefringence pattern builder according to claim 19, wherein the retardation disappearance temperature after rising is not in a temperature range of 250 ° C. or lower. 21. The birefringence pattern builder according to claim 19, wherein the in-plane retardation at 20 ° C. is 10 nm or more. 20. The optically anisotropic layer is formed by applying and drying a solution containing a liquid crystalline compound having at least one reactive group to form a liquid crystal phase, and then polymerizing and fixing by irradiation with heat or ionizing radiation. The birefringence pattern builder according to any one of ˜21. The birefringence pattern builder according to claim 22, wherein the liquid crystal compound has at least a radical reactive group and a cationic reactive group in the same molecule. The birefringence pattern builder according to claim 23, wherein the radical reactive group is an acryl group and / or a methacryl group, and the cationic group is a vinyl ether group, an oxetane group and / or an epoxy group. A method of manufacturing a substrate for a liquid crystal display device including at least the following steps [101] to [103] in this order:
[101] A liquid crystal compound having at least one reactive group on a substrate is applied and dried to form a liquid crystal phase, and then the liquid crystal phase is irradiated with heat or ionizing radiation to form an optically anisotropic layer. Forming a step;
[102] A step of pattern exposing the optically anisotropic layer;
[103] A step of heating the optically anisotropic layer to 50 ° C. or higher and 400 ° C. or lower. A method of manufacturing a substrate for a liquid crystal display device including at least the following steps [111] to [115] in this order:
[111] A solution containing a liquid crystal compound having at least one reactive group is applied onto a substrate and dried to form a liquid crystal phase, and then the liquid crystal phase is irradiated with heat or ionizing radiation to form an optically anisotropic layer. Forming a step;
[112] A step of forming a photosensitive resin layer on the optically anisotropic layer;
[113] A step of pattern exposing the optically anisotropic layer and the photosensitive resin layer;
[114] A step of removing an unnecessary photosensitive resin layer on the substrate;
[115] A step of heating the optically anisotropic layer to 50 ° C. or higher and 400 ° C. or lower. Manufacturing method of substrate for liquid crystal display device including at least the following steps [121] to [123] in this order:
[121] An optically anisotropic layer obtained by applying and drying a solution containing a liquid crystalline compound having at least one reactive group to form a liquid crystal phase, and then irradiating the liquid crystal phase with heat or ionizing radiation. A step of forming a transfer adhesive layer and an optically anisotropic layer in this order on a substrate using a transfer material having a transfer adhesive layer;
[122] A step of pattern exposing the optically anisotropic layer;
[123] A step of heating the optically anisotropic layer to 50 ° C. or higher and 400 ° C. or lower. A method of manufacturing a substrate for a liquid crystal display device including at least the following steps [131] to [135] in this order:
[131] An optically anisotropic layer obtained by applying and drying a solution containing a liquid crystalline compound having at least one reactive group to form a liquid crystal phase and then irradiating the liquid crystal phase with heat or ionizing radiation; Forming a transfer adhesive layer and an optically anisotropic layer in this order on a substrate using a transfer material having a transfer adhesive layer;
[132] A step of forming a photosensitive resin layer on the optically anisotropic layer;
[133] A step of pattern exposing the optically anisotropic layer and the photosensitive resin layer;
[134] A step of removing an unnecessary photosensitive resin layer on the substrate;
[135] A step of heating the optically anisotropic layer to 50 ° C. or higher and 400 ° C. or lower. Manufacturing method of substrate for liquid crystal display device including at least the following steps [521] to [523] in this order:
[521] A step of forming a transfer adhesive layer and an optically anisotropic layer in this order on a substrate using a transfer material having an optically anisotropic layer made of a stretched film and a transfer adhesive layer;
[522] A step of pattern-exposing the optically anisotropic layer;
[523] A step of heating the optically anisotropic layer to 50 ° C. or higher and 400 ° C. or lower. A method for manufacturing a substrate for a liquid crystal display device including at least the following steps [531] to [535] in this order:
[531] A step of forming a transfer adhesive layer and an optically anisotropic layer in this order on a substrate using a transfer material having an optically anisotropic layer made of a stretched film and a transfer adhesive layer;
[532] A step of forming a photosensitive resin layer on the optically anisotropic layer;
[533] A step of pattern exposing the optically anisotropic layer and the photosensitive resin layer;
[534] A step of removing an unnecessary photosensitive resin layer on the substrate;
[535] A step of heating the optically anisotropic layer to 50 ° C. or higher and 400 ° C. or lower. A substrate for a liquid crystal display device obtained by the production method according to any one of claims 25 to 30. 32. The substrate for a liquid crystal display device according to claim 31, comprising an optically anisotropic layer having a region of in-plane retardation Re1 and a region of in-plane retardation Re2 (where Re1> Re2). The substrate for liquid crystal display device according to claim 32, wherein Re2 is 5 nm or less. A liquid crystal display device comprising the substrate for a liquid crystal display device according to any one of claims 31 to 33. The liquid crystal display device according to claim 34, wherein the liquid crystal mode is a transflective mode.

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